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Chem. Rev.

1988, 8 6 , 709-730 709

Ab Initio Calculations of Vibrational Spectra and Their Use in the

Identification of Unusual Molecules


Department of Chemistry, Vanderbilt Universiv, Nashville, Tennessee 37235


J. Heyrovskp Institute of Physical Chemistrv and Eiectrochemistry, Czechoslovak Academy of Sciences, Michova 7,
12 1 38 Prague 2, Czechoslovakia

Received December 12, 1985 (Revised Manuscript Received March 27, 1986)

Contents structures. Compare experimental and theoretical

spectra, and accept or reject the assumed structure on
I. Introduction 709 the basis of agreement or disagreement between the
I I. Theoretical Approaches to Vibrational Spectra 71 1 two.
A. Harmonic Approximation 71 1 Historically, quantum chemistry had an impact first
8. Perturbation Treatment of Anharmonicky 712 in the field of electronic spectroscopy. In the late fiiies
C. Classification of ab Initio Calculations 713
and early sixties the quantum chemistry of all but the
simplest systems was dominated by semiempirical
111. Computation of IR Spectra 714 techniques such as the Pariser-Parr-Pople (PPP)me-
A. Force Constants and Frequencies 714 thod.' Calculations of this type were applied mostly in
B. Intensities 715 the field of electronic spectroscopy to interpret the
C. Use of Empirical Parameters 716 electronic spectra of conjugated a-electron systems. An
IV. A Test of the Method 717 example,2the main goal of which was structure deter-
V. Examples of Appiicatlons 718
mination, concerns the benzenoid hydrocarbon zethrene
(I). A hydrocarbon to which the structure of zethrene
A. HNO 718 was originally assigned was actually either a derivative

B. Cyciobutadiene 719 of acepleiadiene (11) or the hydrocarbon (111). Com-
C. [l.l.l]Propeilane 722
D. Methylenecyciopropene 722
E. Cyciopropenyiidene 723
F. Thiirene 723
VI. Some Predictions of I R Spectra of Unknown 723
VII. Compilation of ab Initio Vibrational 726
V I I I . Summary 726

I. Introductlon 00 00 00
The synthesis of new compounds and the determi-
nation of their structures is one of the main goals in I II Ill
chemistry. In recent decades various kinds of spec-
troscopy have played a major role in structural deter-
mination. Apart from the direct determination of parison of theoretical spectral data for 1-111 with two
structure by means of X-ray analysis, the most useful available absorption curves showed that the assumed
among these spectroscopies are electronic (ultraviolet zethrene was actually I11 and that a newly synthesized
and visible), vibrational (infrared and Raman), nuclear hydrocarbon was really zethrene.
magnetic resonance, and mass spectrometry. Since the 1960s the development of larger and faster
A full use of experimental spectroscopy for the pur- computers together with elaborate ab initio programs
pose of structure determination requires the availability has allowed the routine computation of theoretical vi-
of a theoretical tool that can provide computed spectral brational spectra for molecules of up to, at present,
data in a completely independent way and with an about ten first-row atoms. During the same period the
accuracy sufficient for a meaningful comparison with availability of low-temperature matrix isolation has
the experimental data. An ideal procedure is the fol- made it possible to isolate highly reactive molecules and
lowing. First record the spectrum of a compound of to obtain their spectra. This technique coupled with
unknown structure. Assign to it one or more plausible the advent of Fourier-transform IR spectroscopy has
structures, and compute theoretical spectra for all these provided a powerful new tool to the experimentalist.

0 1986 American Chemical Society

710 Chemical Reviews. 1966. Vol. 86. No. 4 Hess et al.

Rudolf Zahradnk was barn 1928 and graduated from th9 Prague
Institute of Technology (1952). I n 1956 he received his C.Sc.
w ee (appoximately equivalent to Ph.D.). and in 1968. the D.Sc.
B. Andes Hess. Jr.. is Professor and Chahman of the Deprmwmt &gee; he then became Assodate Professor Of Charles vntvenny.
of Chemistry a1 Vanderbill University. He was bom h WMngton. At present he is the Head of the Group of Theay of the Chemical
DE, in 1940. received a B.A. (Wllllams College) In 1982. an M.S. Reactivity in J. Heyrovskg Institute of Physical Chemistry and
(Yale) h 1963. and a W.D. (Yale) in 1966 under Professor Kenneth Electrochemistry. Czechoslovak Academy of Sciences. Prague.
B. Wberg. After two years of postdoctoralstudles wiih Professor From 1965 to 1984 he spent several periods as visiting professor
Vkgil BoekelheMe at the University of Oregon. he plned the De- at universities in Wuzburg. Darmstadt. Groningen. Giessen. Basb.
partment of Chemistry at Vanderbin University as an assistant Sandal. Osaka. Erlangen. and Leipzig. I n 1970 he received a NSF
professor in 1968. He spent a year (1973-1974) at the H e y o w (Washington) senior fellowship. I n 1981 he was elected in the
Institute. Czechoslovak Academy of Sciences. Prague wnh Dr. International Academy of Quantum Molecular Sciences. He acts
Rudolf Zahradnik as a National Academy of Sclences Exchange as a member of ediorial boards of Journal of Molecular slrucfure
Scientist. His research interests include the thmry of aromaticity. (THEOCHEM). Reactiviiy and Structure (Springer). and Chemical
ab initio wmputatbn of vibratonal spectra and tkaetkal shdies Reviews, and is a member pf the advisoly board of Theorefica
of organic reaction mechanisms. Chemica Acta. Dr. Zahradnik has authored or coauthored about
300 papers, a number of textbooks. and 7 books. These works
deal mainly wiih molecular orbital theory. theory of chemical re-
activity. and weak intermolecular interactions in chemistry and

- .
For example the highly reactive thiirene was prepared
by the following ~ c h e m e . ~

1 L

LJ. schaad.WhosereJearch h i e r e s b a r e h ~ c h e m l s b y . Also present in the product mixture were ethynyl

b ~ofessorof Chemistry. varderbin university. ashv vine. TN. ~e
was ban (1930) h cokmbus.OH. W A.B. deqee is I "Harvard mercaptan and thioketene. IR spectroscopy was the
h 1952. and his W.D. was done at the Massachusetts 1" of tool by which the presence of thiirene was identified.
Technology under the direction of C. G. Swain. After postdoaoral A spectrum of a reaction mixture obtained by the de-
study wiih C. A. Coulson (Oxford) and Harrison Shuil (Indiana). he composition of thiadiazol is shown in Figure l. It is
joined Vanderbin University in 1961.
to be expected that the spectra so obtained are of low
rmlution and that the assignment is uncertain because
of side product formation.
The aim of this review is to show the utility of the-
oretical vibrational spectra in such experiments. It
tums out that the accuracy of these spectra is sufficient
to give correct overall patterns, but fine details are not
yet to be trusted. The next sections outline the theo-
retical background of vibrational calculations. A
practical chemist, whose interest is seeing whether
theoretical vibrational spectra can be of use to him,
might profitably skip these sections at first reading and
turn to the examples of sections IV and V. Such readers
MEBrsky was t a n h 1942 h slavakla and he hk R N X
should however keep in mind the distinction between
from Charles University in Prague in 1964. He then !dmd Dr. two ways of calculating vibrational spectra. In both a
Zakadnik's gwp at the Czechoslovak Academy of sdenees and force constant matrix is diagonalized to give molecular
received his CSc. (equivalent to Ph.D.) in 1968. He was a post- vibrational frequencies. In the ab initio method of this
doctoral fellow at the University of Winburg (1968) and visning review, these force constanta are derived by as rigorous
professor at Vanderbin University in Nashville (1982) end Pasteu
University in Strasboug (1984). His research interests Center on as possible a solution of the electronic SchrBdinger
chmkal a m t i o m of molecu$r Uway and computational equation of the molecule in the fixed-nucleus approx-
chemistry. imation. In the other method, which is older and more
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 711

systems such as liquids, clusters, or floppy molecules,

for which normal mode analysis is inappropriate. The
subject of the review by Schrader, Bougeard, and Nig-
gemann6 is most closely related to our paper. It also
deals with structure determination by infrared and
Raman spectra. Their review is however more general,
and the results of only a few ab initio calculations are
presented as illustrative examples. Recent reviews by
0 I I I 1
Fogarasi and Pulay7 summarize the progress made in
3000 2000 1600 I200 800 the last several years in ab initio methods and compu-
c m-1 tational techniques (analytical computation of second
Figure 1. Infrared spectrum of the photolyzed thiadiazole? The and higher derivatives of energy, basis set and corre-
arrows mark bands assigned to thiirene. lations effects), and are recommended as an extension
of our sections IIC and IIIA.

I I . Theoretlcal Approaches to Vlbratlonal


A. Harmonic Approximatlon
Consider the Schrodinger equation for a polyatomic
molecule with M nuclei and N electrons

c c- rab
@>a a=i j>i i=irjj

where ma and 2, are the mass and charge (in units of

bond length - electron charge) of nucleus a,m, and e are the electronic
mass and charge, ria is the distance between electron
Figure 2. Schematic representation of a potential curve from i and nucleus a,and rij and ra6are defined analogously.
the fixed nucleus calculation (solid line) and ita harmonic ap-
proximation (dashed line). The terms on the left of eq 1give, in order, the kinetic
energy of the nuclei, that of the electrons, the elec-
tron-nuclear attraction, the nuclear-nuclear repulsion,
usual among experimental spectroscopists, the force and the electron-electron repulsion. The wavefunction
constants are simply guessed. This older method can depends upon the 3(M + N) coordinates of the
be useful if the molecule studied is similar enough to electrons and nuclei. Since the nuclei are heavier and
others with known force constants, but since there are move more slowly than the electrons, it is usual to
usually more force constants than vibration frequencies, neglect the nuclear kinetic energy term in eq 1 by
there are many ways to choose force constants to pro- holding the nuclei stationary. The resulting equation
duce exact agreement with experimental frequencies. describes the motion of the N electrons in the field of
It is common to find in the literature a molecule studied the fured nuclei, and the energy E of these electrons will
by two groups who have produced different, but equally depend upon the chosen relative nuclear positions. In
accurate and equally plausible, sets of force constants. the case of a diatomic molecule there is only a single
One application of ab initio vibrational calculations is relative position, the bond length Ri2;and the plot of
in the choice between these sets of experimental force E(R12)w. R12will be as shown by the solid line in Figure
constants. However it is in the case of unusual mole- 2. For a polyatomic molecule the electronic energy in
cules, such as reactive intermediates, where analogies this fixed-nuclear approximation will depend on all
are poor and guessed force constants particularly nuclear positions so that E = E(Ri...RM),though E is
doubtful, that we suggest ab initio calculations will be constant for those combinations of nuclear displace-
of greatest use. ments that give translation or rotation of the molecule
There are several review articles in the literature with as a whole.
titles similar to ours though their scope is different. As Born and Oppenheimer8showed that if the nuclear
stated by Schutte4the purpose of his paper is "to ex- kinetic energy is treated as a perturbation on the fix-
amine the progress which has been made since 1926 in ed-nuclear Hamiltonian, the first-order energy correc-
the ab initio calculation of both the vibrational fre- tion vanishes at all positions of nuclear equilibrium (i.e.,
quencies of molecules as well as the forces acting upon for stable molecules). The second-order energy cor-
individual atoms when the equilibrium of the molecule rection is given by an equation describing the nuclear
has been disturbed". Molecular orbital calculations are motion
dealt with only very briefly, and the paper concerns
mostly diatomic molecules. A review by Fredkin, Ko-
mornicki, White, and Wilson5focuses on treatment of
712 Chemical Reviews, 1980, Vol. 80, No. 4 Hess et al.

where the first term in eq 2 is the kinetic energy op- TABLE I. Harmonic and Anharmonic Vibrational
erator for the nuclei and E,, is the second-order energy Frequencies (cm-') of the HCOOH Molecule Given by ab
Initio SCF 4-31G Calculations"
correction and gives the energy of the nuclear motion.
The potential V(R,...RM)consists of the quadratic terms obsd
frequency, calcd frequency (cm-')
in a power series expansion of E(R l...RM)about the mode cm-' harmonic anharmonic
equilibrium position, OH 3570 3769 3629
CH 2944 3160 3047
c=o 1776 1909 1882

- 1-
1 3M a2E
2 ij=ldxiaxj
+ ... ( 3 )
where X1,
X 2 . . X m are the Cartesian coordinates of the Reference 13.
A4 nuclei. The first term E(X10...X3Mo) adds only a
constant to all allowed E,, and can be ignored for the
purposes of mqst vibrational calculations. Since E is be no nonredundant set of simple internal coordinates.
a minimum at the equilibrium geometry, all All of this is taken care of in the commonly used GF
matrix formulation of the vibrational problem by
6. Perturbation Treatment of Anharmonicity
and the second term in eq 3 vanishes. If all terms of Most of the vibrational calculations discussed in
order higher than second are neglected, the potential sections IV-VI and listed in Tables IV and V have used
is a quadratic function of the nuclear displacements AXi the harmonic approximation of eq 4, but in recent years
1 3M there has been progress in the ab initio calculation of
E(X1...X3M) - Fii AXiAXj V(R1...R M ) (4) cubic and quartic force coestants. These are the third
2 lJ'1
and fourth order terms that were dropped from eq 3,
where the force constants Fij are given by and their availability allows the possibility of including
F.. =
a2E I (5)
anharmonicity in ab initio treatments of the vibrational
problem. Prior to 1980 this was rarely done, but one
may anticipate it being done more commonly in the
near future. Perturbation theory yields the following
Equation 4 is known as the harmonic approximation.
In the diatomic case this corresponds to replacing the formula for the anharm0nicity:'O
solid curve of Figure 2 by the parabola shown by the 1 1
dashed line. As can be seen, this approximation may xrr = 16 4ww - 16 C4,2[(8 4 - 3 d ) / ~ s ( 4
4 -4 1
be satisfactory for small displacements from the equi- (7)
librium position R120,but it cannot be accurate for large
distortions of the molecule. Equation 7 contains the quadratic, diagonal and sem-
A transformation to mass-weighted coordinates, pi = idiagonal cubic, and diagonal quartic force constants.
(mi)*/2AXi,followed by rotation of the coordinates to The wk are the harmonic frequencies. The quartic
coincide with the principal axes of the quadratic form constant +rm may be estimated easily1' (for stretching
in eq 4, gives an expression for V containing only vibrations) or it may be calculated numerically.
squared terms Equation 7 does not yield anharmonicities of high ac-
1 3M curacy, but it represents the only method suitable for
practical application to polyatomic molecules of arbi-
trary structure. Equation 7 is relatively simple. The
where the Q, are coordinates relative to the principal only complication met in the calculation of xW is that
axes and are called "normal coordinates". As a result the force constants 4- and 4- are derivatives of energy
of these transformations eq 2, which depends on 3M with respect to normal coordinates. They are not
variables, separates into 3M equations, each depending therefore force constants obtained by the differentiation
upon a single Q,. Further, each of these is a harmonic of energy with respect to internal coordinates (J"and
oscillator equation with force constant hi.
For a nonlinear polyatomic molecule there turn out
to be six of the A, with value zero. These correspond
F,, in the notation of the next sections). The conver-
sion F 4 may be performed by a rather complicated
nonlinear transformation.12 Alternatively, 4w8may be
to the three translational motions and three rotations obtained from the changes of the energy gradient along
of the entire molecule. The six zero-frequency motions normal coordinates. This way of obtaining 4rrsis con-
can be removed by working in a coordinate system with ceptually simple, but computationally it is not eco-
the origin at the center of mass and rotating with the nomic.
molecule. The remaining 3M - 6 degrees of freedom We have selected two examples of the ab initio cal-
are usually specified by internal coordinates such as culation of anharmonicity by means of eq 7. The fiist13
bond lengths and bond angles. As a result, fewer force is for the formic acid molecule. The level of the ab initio
constants need be evaluated, and those that are evalu- calculations was modest, so only a rather approximate
ated have chemical interpretation. Minor difficulties potential was obtained. From the results presented in
arise because the transforrqation to these coordinates Table I it is seen that the inclusion of anharmonicity
is not linear except in the limit of infinitesimal dis- by means of eq 7 leads to better agreement between
placements, and because in particular cases there may theory and experiment, though the error in the com-
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 713

TABLE 11. Vibrational Wavenumbers (cm-’) of the Water Molecule Given by ab Initio Calculations
u1 02 03 expt4 eq 7 var calcn var calcn
0 1 0 1b95 1649 (1670) 1625 1623
0 2 0 3152 3261 3211
1 0 0 3657 3619 (3869) 3714 3667
0 0 1 3756 3753 (3980) 3814 3752
0 3 0 4667 4835 4759
1 1 0 5235 5253 5320
0 1 1 5331 5448 5426
(IFor references to experimental data see quoted theoretical papers. Potential obtained by CI-SDQ calculation^,^^ anharmonicities from
eq 7, harmonic frequencies in parenthesis. CTakenfrom ref 15; potential obtained by CEPA calculation,16vibrational frequencies by a
variation method; the frequencies were read from a figure in ref 15, so the fourth digits in the entires may be uncertain. dTaken from ref
17: potential obtained by MRCI-SD calculation^,^^ vibrational frequencies by a variational method.

puted frequencies is still considerable owing to the ap-

proximate potential. The second example concerns the
water molecule. Table I1 shows the results of three ab
initio studies of this molecule, all using very large basis
sets. They differ in the post-Hartree-Fock part of the
calculation and in the method used for the calculation
of the anharmonic frequencies. Hennig, Kraemer,
Diercksen, and Strey14carried out a configuration in-
teraction calculation with singly and doubly excited
configurations and used Davidson’s formula for esti-
mating the contribution of quadruple excitations. The
resulting potential was used with eq 7 for the anhar-
monicity. The computational effort was much greater
than in the example of Table I, but the error is still
rather large. One might suppose this error to be due
to the approximate nature of eq 7. However, Bot-
schwina15has performed calculations with a potentialls
bond length -
of comparable quality and used the more sophisticated Figure 3. Schematic representation of potential curves given by
method of vibrational configuration interaction for the ab initio calculations for a diatomic molecule at three levels of
sophistication: SCF, small basis set (dotted line); SCF, large basis
evaluation of the frequencies. He did not obtain better set (dashed line); large basis set with electron correlation (solid
agreement with experiment. Recent ab initio calcula- line).
tions17J8on the water molecule show that it is necessary
to go beyond the CI-SD(Q) level of ref 14 if frequencies
of high accuracy are to be obtained. Sexton and calculations with medium and large basis sets, (3) me-
Handy17applied the vibrational variation method to the dium and (preferably) large basis set calculations with
potential from their multireference configuration in- the inclusion of electron correlation. This rough clas-
teraction calculation with single and double excitations sification of ab initio calculations, which refers only to
(MRCI-SD). Their calculated fundamental frequencies the calculated potential, permits us to formulate a
are in error by only 28 cm-’ for the bend and 10 cm-’ general dependence of the accuracy of computed vi-
and 4 cm-l for the two stretches. They also improved brational frequencies on the type of ab initio calcula-
the analytic representation of the MRCI-SD surface of tion.
Kraemer, ROOS,and Siegbahn18and arrived at funda- SCF calculations are known to give a good account
mental frequencies that are in error by only 22, -3, and of the energy hypersurface only in the region close to
1 cm-l. the equilibrium molecular geometry. At larger devia-
Most of the molecules to be discussed in this review tions from the minimum, the SCF potential curve starts
are larger than water, and computations of the accuracy to depart considerably from the “experimentay curve
just described are not yet possible for them. Frequency because of the neglect of electron correlation. The
errors of 5-10% will be usual. In spite of these large simplest case-the case of a diatomic molecule-is
errors the overall pattern &e., relative frequencies and schematically presented in Figure 3 for the three levels
relative intensities) of the computed spectra usually of calculation above. As this figure shows, the SCF
resemble those of the observed spectra sufficiently to curve is too steep. This implies the force constant at
be of help to the experimentalist. the SCF level will be too high and also the computed
vibrational frequency will be too high. The smaller the
C. Classiflcatlon of ab Inltlo Calculations basis set, the more profound is this effect. Electron
correlation will lower the curve toward the exact solid
Accumulated experience suggests that the accuracy curve of Figure 3. However even the exact curve, if
of calculated vibrational frequencies is affected more replaced by the harmonic approximation of Figure 2,
by the quality of the calculated potential than by the will give too high frequencies since the approximating
inclusion of anharmonicity. For this reason we consider parabola rises too steeply at large distances. These
it useful to classify ab initio as follows: arguments concern the potential curves €or stretching
(1) SCF calculations with a small basis set, (2) SCF vibrations, but it has been found empirically that the
714 Chemical Reviews, 1986, Vol. 86, No. 4


Hess et al.

where f k is a force (the negative of a component of the

gradient) acting along the kth coordinate and Ak is the
deviation from the reference geometry along the kth
coordinate. In eq 8 the first differentiation of eq 5 is
performed analytically and the second one numerically.
Cubic diagonal and semidiagonal force constants


I . , I may be obtained by a single numerical differentiation

of analytic quadratic force constants analogous to eq
8 or by a double numerical differentiation of the com-
ponents of the force1lPz6
I I 1 (( I I I I I
3600 3200 2800 22 2000 1600 1200 800 400


where the first term on the right hand side is the force
Figure 4. The infrared spectrum of cyclobutadiene compared at the reference geometry. Much of the initial devel-
with results of ab initio calculation^^^ at three levels of sophis-
tication. Intensities were not computed in the MP2 work. opment of this computational method was done by P.
Pulayz6 who is the author of the program TEXASz7
same trends hold for bending modes. Figure 4 shows designed especially for this purpose. One may find all
the example of cyclob~tadiene,~~ where the three cal- information necessary for the effective computation in
culations described as 4-31G, 6-31G*, and MP2/6-31G* papers by Pulay (particularly in ref 11 and 26). We
correspond to the three levels of classification above. restrict ourselves here to noting that the force constants
If one ignores the two C-H stretches at high frequency in eq 8 and 10 should be expressed in symmetrized
which, because of the complexity of the matrix isolation internal coordinates and not in Cartesian coordinates.
spectrum in the C-H region, have not yet been iden- This reduces the cost considerably. The most efficient
use of symmetry coordinates was described by Hehre
tified experimentally, all calculated frequencies are too and co-workersB recently, though the method was used
high in the 4-31G calculation. When the basis is im-
proved to 6-31G* all frequencies, except the second a decade earlier by Pulay.% Cartesian coordinates are
lowest, decrease, but are still too high. Inclusion of used for example in standard runs in the HOND05
electron correlation in MP2/6-31G* lowers the fre- program. This is convenient from the point of view of
quencies still further. preparation of the input data, but the cost is excessive
even with relatively small basis sets.
A calculation of the theoretical spectrum of a poly-
I I I . Computation of I R Spectra atomic molecule as outlined above requires a rather
large amount of computer time and human effort. The
This section gives practical details for the ab initio analytical calculation of force constants might be ex-
calculation of theoretical infrared spectra. Section IIIA pected to lessen this work. The first practical method
discusses the effective computation of quadratic and for the analytical calculation of force constants was
cubic force constants. Section IIIB describes the cal- developed by Pople and c o - ~ o r k e r s and, ~ ~now
~ ~ ~ex-
culation of intensities. The example of the water pressions are available for the third3zand higher de-
molecule, noted in section IIB and summarized in Table rivatives within SCF theory. In spite of this progress,
11, indicates that even the most sophisticated ab initio practical application of these higher derivatives is lim-
calculations are not able to compete in accuracy with ited by the requirement of enormous amounts of disc
high-resolution experiments. In practical applications space. The situation seems to be similar with correlated
one might wish therefore to adopt a strategy in which wave functions. Pople, Krishnan, Schlegel, and Bink-
one does not insist so strictly on the nonempirical na- ley's second-order Merller-Plesset treatmentm contained
ture of calculations. This will be discussed in section the first practical scheme for the analytical computation
IIIC. of the energy gradient for a correlated wave function.
Expressions have been given since33-36for up to
A. Force Constants and Frequencles fourth-order derivatives of energy within the C137and
MCSCF%framework. Efficient algorithms are however
Modern programs for ab initio SCF calculations still lacking, so if one wishes to go beyond the Har-
contain packages for the analytical calculation of the tree-Fock level, a force field of the form
energy gradient or, in some programs, for the analytic
calculation of the quadratic force constants. If quad-
ratic force constants (eq 5) are not computed analyti-
cally by the program, they may be obtained from the
energy gradient using the has to be assumed, and a set of energies fitted to it
Fij x [ fJ. ( 41 = -Ai) - fj(qi = +Ai)]/2Ai numerically (by least-squares). In common applications
the expansion ( 1 1 ) is truncated at the quadratic term
(harmonic approximation).
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 715

B. Intensities

Integrated infrared band intensity for the kth fun-

damental is definedg as

where C is concentration (mol L-'), L is optical path

length (cm), and Io and I , respectively, are the inten-
sities of the incident and transmitted light. Assuming
electric and mechanical harmonicity, Ak may be ap-
p r ~ x i m a t e dby


where NA is Avogadro's number (mol-l), c is the light

velocity (cm d),gk is the degeneracy factor, and dp/dQk BZUBlU

is the dipole-moment derivative with respect to the kth

normal coordinate Qk. The derivative dp/aQk must be CM"
expressed in ~ ms-', ~so that
/ ~Ak be expressed in cm-2 Figure 5. Theoretical infrared spectra of ethylene computed using
L mol-', as in eq 12. Programs for ab initio calculations an 6-31G* basis. Direct calculation of the intensity by eq 13-15
yield however the derivatives d p / d Q k in non-SI units is shown at the bottom. The top shows intensities using eq 17
D k1U-1/2,where U is the unified atomic mass unit and an approximately constant field caused by point charges. The
M(12C)/12 = 1.660565 X kg. Transformation to A, intensities are exaggerated.
~ ms-' ~is performed
/ ~ by m ~ l t i p l y i n gthe
~ ~derivatives
by 0.7760184 X lo2. In actual calculations one first
evaluates numerically the derivatives of the dipole lecular energy since they are used in the geometry op-
moment with respect to symmetry internal coordinates timization. Therefore instead of (3N-6) computations
of the dipole moment to get the (apj/t3qi),one need do
ar/dqi [r(qi = + Ai) - P(qi = -AJ]/2Ai (14) only three computations of the energy gradient in a
constant electric field to compute all a2E/dF,aqi,
Transformation from dp/dqi to a p / a Q k is performed by
means of the expression a2E/aF,,aqiand d2E/aFzaqi.
Bacskay, Saeber, and Taylor41describe a program for
computing the energy of a molecule in a constant field
and for implementing the Komornicki and McIver
suggestion. Actually this program revision need not be
where L is the matrix for the transformation of normal done in many ~ases.4~ Many molecular energy programs
coordinates to symmetry coordinates and is obtained such as GAUSSIAN 8243will allow the use of nuclei of
from the GF matrix method. For isotopic derivatives either positive or negative charge, with or without as-
of molecules having a nonzero dipole moment, a rota- sociated orbitals. A constant electric field at a molecule
tional correction of the dipole moment derivatives must can be approximated by placing two large bare charges
be taken into account." of equal magnitude and opposite signs at equally large
Komornicki and McIveP have shown how the com- distances but in opposite directions from the molecule.
putation of infrared intensities can be carried out in an GAUSSIAN 82 requires no reprogramming to treat this
efficient way that makes use of the energy gradient. system which it views as an ordinary molecule with no
The j component of the dipole moment vector of a external field. Figure 5 shows the results of such an
system of fixed charges is given by approximate intensity calculation on ethylene. This
method should have no advantage in speed or accuracy
over Bacskay's program. It merely avoids reprogram-
ming of the molecular energy calculation.
where E is the energy of the system in a constant For correlated wave functions the dipole moment
electric field F, sufficiently weak that polarization, i.e., derivatives are usually calculated numerically for eq 14
rearrangement of the charges in response to the field, in which the dipole moments for the two structures at
can be neglected. Then taking the derivative of eq 16 qi = +Ai and qi = -Ai are obtained by a finite-field
with respect to the coordinate qi, and interchanging method. Essentially this means the use of eq 16 since
order of differentiation on the right gives the energy of a molecule in an external field is assumed
in the form of a power series
E(F) = E(0)- CpjFj - - CajgjFk + ... (18)
I 2 jk
The quantities apj/dqi on the left of eq 17 are those and pj is again obtained nUmericall+45 from E(Fj)and
needed in eq 15 for the computation of infrared inten- E(-Fj). In the evaluation of E(F) one first carries out
sities. The quantities (dE/aqi)are the components of the so called coupled Hartree-Fock calculation to get
the energy gradient. These are already available in field-dependent SCF molecular orbitals, which are then
most programs for the computation of the SCF mo- sed^^-^^ as input for the calculation of E(Fj) by
716 Chemical Revlews, 1986, Vol. 86, No. 4 Hess et 81.

standard (field independent) expressions for the cor-

relation energy.
In spite of the fact that intensities are very important
for the interpretation of IR spectra and that their
calculation at the SCF level requires practically no extra
computer time, they have not been commonly com-
puted. Raman intensities are computed still less fre- EXPL GEOM
quently. These may be c ~ m p u t e by d ~a ~direct
~ ~ ~cal- I I I

culation of polarizabilities from elements of the elec-

tronic transition moment. This approach gives however
rather poor results, unless a large basis set is used. As
for any electric property it is therefore preferable to use
special basis sets designed for this p u r p ~ s e .In~ ~ ~ ~ ~
calculations beyond the Hartree-Fock level the deriv-
atives of polarizabilities are obtained as shown above
for dipole moment derivatives: polarizabilities by a
finite-field and their derivatives by nu-

merical differentiation. Komornicki and McIver's em .'
method used with a point charge field should also have
application in the calculation of Raman intensities, Figure 6. Comparison of 3-21G computed frequencies and in-
tensities (see text) of ethylene with those of experiment.
though problems with numerical accuracy are expected
to be more severe here than for infrared intensities.
bending force constants. Blom and Altona59@*M965 have
C. Use of Empirical Parameters proposed a much more elaborate scheme of scale fac-
tors. Based on the experimental spectra of ethane,
The computation of the vibrational spectrum of a propane, cyclopropane, ethylene, and dimethy1 ether
polyatomic molecule of even modest size is lengthy, and they proposed scale factors (4-31G basis set) for the
one may be forced to work at the SCF level with a small various types of stretches, bends, torsions, and wags.
basis set. In such a case, one must count on a large In addition they suggested a single scale factor to be
overestimation of calculated vibrational frequencies. applied to all off-diagonal force constants. With these
Several simple (more or less) empirical ways have been scale factors they were able to reproduce experimental
suggested to reduce this error. The first is a proposal spectra with an error of less than 1%. Pulay, Fogarasi,
by S ~ h w e n d e m a nto~ compute
~ force constants at ex- and Boggs@~~~ have proposed a set of standard diagonal
perimental geometry rather than at the minimum en- force constant scale factors for their 4-21G basis set
ergy geometry of the basis set used. This need not based on the spectra of glyoxal, acrolein, butadiene,
n e ~ e s s a r i l ylead
~ ~ *to
~ ~improved values of the force ethylene, formaldehyde, and benzene. Their treatment
constants, though experience shows that it often of the off-diagonal scale factors differed from that of
does.54-57Schwendeman's proposal also shortens the Blom and Altona in that they proposed all off-diagonal
computations since the geometry optimization step is force constants (FJ should be scaled by (CiCj)l12 where
dropped. Ciand Cj are the scale factors for Fii and Fjj. Finally
Pulay and collaborators as well as Blom and Altona Bock, George, and Trachtman have also proposed a set
have suggested that even experimental geometries can of scale factors for the 4-31G basis It is note-
sometimes lead to difficulties due to errors in these worthy that useful results may also be obtained by
geometries. Blom and Altona have therefore proposed applying scaling factors to semiempirical calculations
corrections to be applied to various bond distances and of the CNDO type.70371This is important with treat-
angles obtained theoretically with Pople's 4-31G basis ments of large molecules for which ab initio calculations
Pulay and collaborators have done the same are not feasible. If one insists on a strict nonempirical
for Pulay's 4-21G basis 5et.l' Corrections for additional nature of the treatment, the diagonal force constants
bonds have also been proposed.61 may be recomputed by means of a more sophisticated
It has also been found that basis set and electron approach (using a larger basis set and with the inclusion
correlation effects are more important for diagonal force of electron correlation).
constants than they are for most coupling force con- However, if one computes both frequencies and in-
s t a n t ~A. ~force
~ field given by SCF calculations may tensities we contend that useful results can be obtained
therefore be improved considerably if the diagonal of by computing the spectrum at the optimized geometry
the force constant matrix is replaced by data originating of the basis set used and without employing scale fac-
from some other source. There are several possibilities, tors. This is important to note since for unusual and
and the choice depends on the user's taste. One may reactive molecules the experimental geometry may be
use experimental data obtained in some independent unknown and standard geometry scaling factors would
way for diagonal force constants, or the computed di- not be applicable. In Figure 6 are plotted (from bottom
agonal force constants may be reduced by empirical to top) the experimental IR spectrum of ethylene, its
scaling factors (typical values range from 0.8 to 0.9). To spectrum computed with the 3-21G basis set at the
some extent scaling factors also account empirically for experimental geometry and scaled with the scale fadon
anharmonicity. In the simplest instance Pulay and proposed by Pulay, Fogarasi, and B ~ g g for s ~the~ 4-21G
M e ~ e r ~ 'suggested
"~ a single scaling of 0.9 for all diag- basis set, the unscaled spectrum computed at the ex-
onal stretching force constants and 0.8 for diagonal perimental geometry, and f m d y the unscaled spectrum
Calculatlons of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 717


II MP2/6-31G’
I I1
I1 6-3lG“
I I I II 6-3iG”MP2 I I Il1I I I
A i B z A i Bz AI AI AiBiBzBzAlBz BI
I I I // I I I I I
4-31G 3600 3200 2600 )7 2000 1600 1200 600 400
I 1 I
cm .’

I 1
I I Figure 8. Comparison of computed IR spectra of cyclopropene
with that of experiment. 6-31G**
reference 76.
and experimental data are from

STO-3G parison of computed spectra with the spectra of a series

of well-characterized systems. This has already been
done in part for ethylene in section IIIC. In that case


// I I
it was shown that the experimental pattern could be
reproduced without relying on empirical parameters.
As a consequence, the vibrational spectra of molecules
to be discussed in this section were all computed at the
3600 3200 2800 )) 2000 1600 1200 800 400

em” optimized geometry for a given basis set and without

employing scale factors.
Figure 7. Comparison of frequencies and intensities of ethylene
computed with various basis sets with those of experiment.“ Figure 7 shows e ~ p e r i m e n t a results
l ~ ~ for ethylene
together with computed frequencies and intensities for
wavefunctions that range from the minimal basis
computed at the 3-21G optimized geometry. The major (STO-3G) to a much larger basis (6-31G**)Y5 A t the
effect of computing the spectrum at the experimental top of the figure the frequencies computed by Pople’s
geometry and using scale factors is to shift the lines to groupmwith partial inclusion of electron correlation by
lower frequency and hence into better agreement with the second-order Maller-Plesset (Mp2) method are also
experiment. Presumably agreement here could be made given (intensities were not computed in this work). It
even better by developing scale factors specifically for is seen that only the STO-3G basis, which gives a poor
the 3-21G basis set. On the other hand, virtually no estimation of the intensities of the C-H stretches fails
effect is seen on computed intensities, and as a conse- to give the observed experimental pattern. In fact at
quence the overall pattern seen at the top of the figure the SCF level, the 3-21G, 4-31G, 6-31G*, and 6-31G**
compares very favorably with that of the experimental results are all very similar. Inclusion of electron cor-
pattern. If one’s task were to confirm the structure or relation does improve computed frequencies signifi-
to make assignments of the various bands in the ex- cantly, particularly in the fingerprint region. However,
perimental spectrum of ethylene, then the spectrum any of the double-zeta SCF results adequately repro-
computed at the optimized geometry without scale duces the experimental pattern of frequencies and in-
factors would be sufficient, This point will be given tensities.
further support by results presented in Section V. Wiberg and collaborator^^^ have computed the IR
Lowe, Alper, Kawiecki, and Stephens72have recently frequencies and intensities of cyclopropene with the
reported frequencies and intensities of ethylene oxide 6-31G** basis set and have measured the experimental
obtained with a 4-31G basis set. These were computed intensities. Frequency assignments had been made
at the experimental geometry of ethylene oxide, and the earlier by Yum and E g g e r ~ .Cyclopropene
~~ provides
force field was also scaled. The effect of scaling was to a more demanding test of the method than ethylene
improve significantly the agreement of computed fre- because it has thirteen IR active modes and in partic-
quencies with experiment; however their computed in- ular because of the presence of seven bands in the fin-
tensities showed little change from those computed with gerprint region compared to only two for ethylene. The
the similar 6-31G basis set without scaling and at the experimental spectrum is plotted in Figure 8 along with
optimum 6-31G geometry.73 Wiberg’s 6-31G** computed spectrum.76 While all
computed absorptions are again shifted to higher fre-
I V . A Test of the Method quency than experiment, the agreement in pattern is
quite good even in the fingerprint region. Lee, Bunge,
Since the main purpose here is to show that the and S~haefer‘~ have also computed the spectrum of
computation of IR spectra can provide assistance to cyclopropene with a double zeta plus polarization basis
experimentalists in confirming the synthesis of unusual set and obtain results very similar to those of Wiberg
systems and/or in making assignments of bands, the and collaborators. The frequencies from our MP2/6-
reliability of the method must be established by com- 31G* 7g calculation (intensities were not computed) are
718 Chemical Reviews, 1986, Vol. 86, No. 4 Hess et al.


.. I I. .I STO-3G
1 I.. .I
I ... I. . I

.. I .
I I I I 6-31G’
1. I. .I I

II EXPT - 1 - L 1 I
. I .I
. . I

3600 3200 2800 2400 2000 1600 1200 800 400
Figure 10. Comparison of computed IR spectraa of thiirane with
Figure 9. Comparison of computed IR spectra73of ethylene oxide that of experiment.
with that of experimentam

presented at the bottom of this figure and show a frequencies at the SCF level were all computed to be
somewhat improved agreement with experiment. higher than observed. Hence if the 6-31G* calculation
The IR spectrum of ethylene oxide has been calcu- had not been done, one would have predicted the C-S
lated with the STO-3G, 6-31G and 6-31G* basis sets by stretch be at a considerably lower frequency than was
Hess, Schaad, and P~lavarapu,’~ and these results are actually observed. Finally it is seen that the 6-31G*
compared in Figure 9 with the experimental spectrum spectrum reproduces the experimental pattern very
by Nakanaga.80 In all three cases the vibrational well. The ordering of frequencies is predicted well, and
spectrum was computed at the optimized geometry for the relative intensities are in excellent agreement with
the basis set. Komornicki, Pauzat, and Ellinger81have experiment.
also reported the calculated frequencies of ethylene
oxide with the 4-31G and 6-31G** basis sets, and their
results compare quite favorably with those of the similar
basis sets 6-31G and 6-31G*. It is seen from Figure 9 V. Examples of ApplkatronS
that again the pattern is well reproduced by the 6-31G*
basis set. In the fingerprint region there are three weak We have selected from the literature a few examples
bands near 1150 cm-l that have not been assigned with showing the present possibilities of ab initio calculations
certainty in the experimental spectrum. The computed of vibrational spectra in their application to the iden-
spectrum predicts very nicely three weak bands in this tification of molecular structures. The harmonic ap-
region. Although the calculated pattern of the fre- proximation was assumed in all cases. We have inten-
quencies of the three bands at the lowest frequency is tionally selected calculations made with the simpler
somewhat different from experiment, the relative in- approaches (SCF,small and medium basis sets) since
tensities allowed assignment of these bands with rea- only such calculations are applicable to larger molecules.
sonable certainty; and the computed assignments do
agree with those assigned from experiment. It is seen
that the 6-31G basis is able to reproduce the experi-
mental spectrum reasonably well. However the STO- A. HNO
3G computed spectrum is in very poor agreement with
experiment, both in computed frequencies and relative An early example of the use of a computed IR spec-
intensities. This was not so much the case for ethylene, trum to confirm the reported observation of a reactive
and it may be that the disagreement here is because molecule is Botschwina’s ab initio calculationm on
ethylene oxide is a polar molecule while ethylene is not. HNO. This molecule was observed in the gas phase as
A related molecule is thiirane. An interpretation of early as 1958 by Dalby,84and it was identified primarily
its experimental spectrum has recently been reported by IR spectroscopy. Prior to Botschwina’s work there
along with the calculation of its spectrum with several had been controversy over the fundamental frequencies
basis sets.82 These results are summarized in Figure 10. and force field of HNO. Jacox and Milligan@reported
In this case the STO-3G spectrum reproduces the ex- a matrix IR spectrum of HNO and several isotopic
perimental pattern surprisingly well. The ordering of derivatives in 1973 and proposed two possible sets of
the frequencies is correctly predicted, and even the force constants (see Table 111). This is not a unusual
intensities are reasonably good. It is interesting to note situation since, as mentioned in the introduction, there
that the intermediate basis set (3-21G), while again are usually infinitely many sets of force constants that
reproducing the intensities fairly well, does lead to some can give the observed frequencies. Not only was Bot-
ambiguity in the frequencies. One band is out of order schwina able to reproduce the frequencies of the parent
(C-C stretch), but perhaps more serious is the fact that molecule and five of its isotopic derivatives quite well
the intense C-S stretch is predicted to be at lower as seen in Table 111, but also to show clearly that the
frequency than observed. In the cases discussed so far, correct force field is B and not A.
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 719

TABLE 111. Force Constants of the HNO Molecule"

I '

force ab initio SCFd

constb assignment A' assignment B' (7S3P/3S)
F* 7.15 4.084 4.536
FRR 10.24 11.035 12.594
(11.335) II
Fa, 0.73 1.337 1.585
FIR 0.236 0.813
Fra 0.106
FRa -0.11 0.749 0.820
nTaken from ref 83. bR refers to the NO bond, r to the NH
bond; force constants are expressed in lo2 n m-", where n is the
number of stretching coordinates. Two different solutions of the
inverse (for references see the original papers3). dThe entries in
parentheses are force constants obtained by applying the scaling
3600 3200 2800 2400 2000 1600 1200 800 400
factors (0.9 for F, and FRRand 0.85 for FaJ.

Figure 11. Calculated2s IR spectra of a 1:l mixture of [1,2-2H2]-

and [ 1,4-2H2]-cyclobutadiene and the spectra observed by
Chapman's group on photolysis of either 2-pyrone-5,6-d2or 2-
B. Cyclobutadiene pyr0ne-3,6-d~~ The open bars show additional weak experimental
lines observed for the mixture by*
Cyclobutadiene has attracted the interest of both
experimental and theoretical chemists since the last
century and provides a nice example of how computed deuteriocyclobutadiene.~~~* Hence the conclusion was
IR spectra can be useful in the identification of unusual that cyclobutadiene is indeed rectangular.
species.% Although Pettit and co-workers had evidence One question however still remained. In 1973
as early as 1965 for the existence of free cyclo- Chapman and co-workers%reported that photolysis of
* ~ not until 1972 (Krantz)sgand 1973
b ~ t a d i e n e , 8it~was IV and V yielded products that had identical spectra.
(Chapman)gothat the first IR spectra were reported for
this molecule. From the IR spectrum both concluded
that cyclobutadiene has a square structure. They re-
ported two strong bands at 570 and 1240 cm-l and a
weak one a t 650 cm-'. At the time Krantz and Chap- IV VI
man prepared cyclobutadiene, the best ab initio calcu-
lation predicted cyclobutadiene to have a rectangular-
singlet ground statesg1 More extensive calculations,
which supported this prediction by Buenker and Pey-
erimhoff, were reported in 1977 and 1978 by three
g r o ~ p s . ~One ~ - ~of~ these (Borden, Davidson, and
Hart)%in fact suggested that the original interpretation
of the IR spectrum might not be correct.
In 1978 Kollmar and Staemmlerg5reported the first They reasoned therefore that this was evidence for a
ab initio calculation of the IR spectrum of cyclo- square structure of cyclobutadiene since IV and V
butadiene using a double zeta + polarization basis set. should have given two different d2-cyclobutadienes(VI
Their results indicated that there should be two strong and VII) if it were rectangular. However, it has been
bands below 2000 cm-l, one at 1377 and the other at 692 shown that, while the observed spectrum (Figure 11)
cm-', which they suggested corresponded to the two does not agree with the computed spectrum of VI or
strong bands observed by Krantz and Chapman in this VII, it does correspond to that of a 1:l ratio of the two
region (the band at 650 cm-' which had earlier been isomers.lW Hence Chapman's group had apparently
assigned to cyclobutadiene had been shown subse- produced not square cyclobutadiene but rather a 1:l
quently by Masamune to be due instead to C02%). In mixture of the two rectangular isomers VI and VII. In
addition they predicted three relatively weak bands at accord with this, Krantz and co-workers had earlier
790, 1129, and 1697 cm-'. shownl0lbthat IV and V are equilibrated with one an-
Later in 1978 Masamunew reported a matrix Fourier other during photolysis prior to conversion to cyclo-
transform IR spectrum of cyclobutadiene which showed butadiene.
remarkably good agreement with the earlier calculation We have learned quite recently that Michl and col-
of Kollmar and Staemmlerg5and with that of Schaad, laborators have been able to identify additional bands
Hess, and Ewig in which an STO-4G basis set was in the IR spectrum of cyclobutadiene and its isotopi-
used.98 Hence the evidence at this point yas strongly cally labelled derivatives.lOla They have located the
in favor of a rectangular striicture. Hess, Cbrsky, and remaining two bands (C-H stretch) in the IR spectrum
Schaad later reported25an improved calculation with of cyclobutadiene at 3107 and 3124 cm-'. They have
the 6-31G* basis set and also with inclusion of electron also assigned eight additional bands in the spectrum of
correlation (MP2), and their results are given in Figure the mixture of the two d2-cyclobutadienes(VI and VII).
4. It is seen that there is remarkable agreement be- These correspond very nicely to bands computed earlier
tween Masamune's observations and the calculated for this mixtureBJmas seen in Figure 11. Finally, Michl
spectra. Similar agreement was found for the tetra- et al. have also obtained the spectrum of the corre-
720 Chemlcal Revlews, 1986, Vol. 86, No. 4 Hess et al.

TABLE LV. Vibrational Calculations of Inorganic Systems

structure type of structure type of
formula or name calcna typeb ref formula or name calcn* type* ref
AlH, AlH, MRD CI Y 118 FHP 4-31G v 163
BH; gQZ- SCF, IEPA/ext Y 119 TC SCF, DZ+P Y 164
BHZ BHZ ST03G Y 120 3-21G v 165
BHZ BHZ CI Y 121 DZ+P v 166
BHO HBO 6-31G*, MP2 Y 122 4-31G Y 167
BeHz BeHz CEPA FC 123 3-21G Y 136
CzSi SiCC CI Y 124 DZ+P Y 168
CClN ClCN ext FC 125 MRD CI Y 169
CClN ClNC ext FC 125 DZ Y 156
CFH HCF 6-31G*, MP2 Y 122 min FC 170
CFN FCN DZ FC 126 6-31G*, MP2 v 122
CFN FCN ext FC 125 TC SCF, DZ+P v 164
CFN FCN 4-31G FC, I 127 3-21G Y 165
CFN FNC ext FC 125 DZ FC 126
CHN HCN 4-31G Y 128 DZ FC 171
CHN HCN CI FC 129 6-31G*, MP2 Y, 1 172
CHN HCN DZ FC 126 6-31G*, MP2 Y, 1 172
CHN HCN DZ Y 130 4-31G Y 173
CHN HCN ext FC 125 CI Y 175, 176
CHN HCN 6-31G** Y, I 132 CI Y, 1 177
CHN HCN 6-31G*, MP2 Y 122, 133 CISD Y 178
CHN HCN DZ+P/CEPA Y 134 6-31G*, MP2 Y 138
CHN HCN 4-31G FC, I 127 ST03G Y 120
CHN HCN SCEP Y 135 6-31G*, MP2 Y 138
CHN HCN 3-21G, 6-31G* Y 136 STOBG, 4-31G FC ,-54

CHN HCN MRD-CI Y, 1 137 CI FC, I 179

CHN HCN 6-31G* Y 138 4-31G Y 180
CHN HCN CISD Y 57, 139 DZ+P Y 168, 181,
CHN HCN CEPA Y 140 182
CHN HCN STO-NG, N-31G I 141 DZ Y 156
CHN HNC ext FC 125 4-21G FC,I 11
CHN HNC 6-31G** Y7 I 132 CI Y, I 46
CHN HNC DZ+P Y 142 ST03G, 3-21G, Y 183
CHN HNC 6-31G*, MP2 U 122 4-31G, 6-21G
CHN HNC CISD Y 144 4-31G U 167
CHN HNC 6-31G* v 138 STOBG, 4-31G Y 185
CHO+ HCO+ 6-31G*, MP2 Y 138 6-31G*, MP2 Y 122
CHO+ HOC+ 6-31G*, MP2 Y 138 ext FC 186
~,Y 14
%HP HCP SCEP, CEPA Y, 1 143 CI I 46
CHP' HCP+ DZ+P Y 142, 143 DZ+P I 49
CHS+ HCS+ 6-31G*, MP2 v 138 3-21G, 6-31G* Y 136
cHs+ HCS+ CEPA Y, 1 145 6-31G* Y 138
CKN KCN ext Y 146 CISD Y 139
CKN KCN ext I 147 MP2, MP3 FC 187
CLiN LiCN ext I 147 MBPT-SDQ. CC
CLiN LiCN ext FC 125 DZ+P v 181
CLiN LiNC ext FC 125 6-31G*, MP2 Y 138
COZ COZ DZ+P FC 149 ST03G, 4-31G FC 54
COZ COZ 4-31G u, 1 150 3-21G, 3-21G* Y 189
COZ COZ CI Y 151 3-21G, 6-31G* Y 190
COZ COZ 4-31G FC, I 127 STOBG, 3-21G, Y 191
COZ COZ 3-21G Y 136 4-31G, 6-21G
coz+ coz+ 4-31G Y, I 150 6-31G*, MP2 Y 138
cos ocs 4-31G FC, I 127 6-31G*, MP2 Y 138
CSZ cs2 4-31G Y, I 150 TC SCF, DZ+P v 164
csz+ cs2+ 4-31G Y, I 150 3-21G Y 165
ClClH- HC1z- min I 152 3-21G Y 192
ClClH- HC1; DZ+P Y 153 CEPA Y, 1 193
ClH2+ CIH2+ 6-31G*, MP2 Y 138 6-31G*, MP2 Y 138
ClHH- HClH- 4-31G, 4-31G**, Y 154 6-31G*, MP2 Y 122
DZ + dif. ext/CEPA FC 194
ClHO HOCl 4-31G, 6-31G**, Y, I 155 DZ Y 83
DZ+P,TZ+P DZ Y 156
ClHO HOCl DZ 1, 156 CAS SCF Y 195
ClNO ONCl ext U 157 6-31G*, MP2 Y 122, 138
ClNO ONCl DZ Y 158 DZ Y 196
ClNS NSCl DZ+P FC 159 4-31G, 6-31G*, Y, 1 155
FzHf HFz+ DZ Y 160 DZ+P. TZ+P
FzH- FHF- DZ Y 161 DZ+P Y 197
FZH- FHF- 4-31G FC 162 ext, CI DZ+P Y 198
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 721

TABLE IV (Continued)
structure type of structure type of
formula or name calcn" typeb ref formula or name calcn" typeb ref
HOSi HSiO 6-31G* v 199 HnP+ PH*+ DZ+P Y 234
6-31G*, MP2 Y 138 Hist SH? 6-31G*, MP2 v 138
CEPA Y, 1 200 H3Si SiH3 3-21G Y 165
6-31G* Y 201 H3Si SiH3 MRD CI Y 235
4-31G FC,I 127 HZCN' HCNH+ 6-31G*, MP2 Y 138
3-21G Y 136 HzLiO+ HzO...Li+ ext Y 236
6-31G* Y 201 HZNZ HNNH CI Y 237
6-31G* Y 201 HZNZ HNNH ST03G, 4-31G Y, 1 238
3-21G, 3-21G*, Y 189 HzNz HNNH 6-31G*, MP2 Y 122, 138
6-31G* HZOZ HZOZ 4-31G Y, 1 239
STO-4G I 202 Hz02 HZ02 6-31G*, MP2 Y 122, 138
TZ+P v 203 HzOz HZ02 DZ FC 240
DZ+P Y 204 HzOSi HzOSi CI, CEPA Y 241
DZ v 205 HzOSi HzSiO 6-31G* Y 199
4-21G FC, I 11 HzOSi HSiOH 6-31G* Y 199
6-31G*, MP2 Y 122. 138 H2Sz HzSz 3-21G*, 6-31G* Y 189
6-31G*, MP2 Y 122' HCLiN+ HCN Li+... DZ,EFV Y, 1 242
3-21G Y 206 HCOz HCOZ 6-31G*, MP2 Y 138
DZ FC 126 HNOz HONO ext Y 243
DZ+P/CEPA Y, 1 207 HNOS HNSO ST03G*, 3-21G*, Y 244
SCEP, CEPA Y, 1 143 6-31G*, MP2, MP3
STO-NG,N-31G I 141 Li202 LizOz DZ+P Y 245
DZ FC 208 Nz02 (Noh DZ Y 246
3-21G, 6-31G* Y 209 NzOz (NO), 4-31G Y 247
3-21G, 6-31G* Y 209 N2OS ONNS 4-31G Y 247
3-21G, 3-21G* Y, 1 211 03s so3 3-21G, 3-21G*, 6-31G* Y 189
6-31G, 6-31G* 4CHz ~ZCHZ DZ, DZ+P Y 249
ext Y, 1 212 AlBr3H3N H3N:AlBr, STO3G Y 250
3-21G, 3-21G* Y 189 AlC13HSN HsNAlC13 ST03G Y 250
STOIG, DZ I 213 AlF3H3N H3NAlF3 ST03G Y 250
DZ FC 171 B2H6 HZBHZBHZ 4-31G FC 251
3-21G Y 136 BZH6 HzBHzBHz 4-31G Y 252
ST03G, DZ I 213 BZH6 HZBHZBHZ 6-31G*, MP2 Y 122, 138
3-21G Y 165 B203 OBOBO DZ+P Y, 1 253
ext/CEPA Y 214 BH4- BHc DZ Y 254
DZ+P Y 215 BeF3Li LiBeF, DZ Y, 1 255
DZ+P, CI Y 216 c302 C3OZ 6-31G* Y 256
DZ FC 217 c2L1Z04 LizCz04 3-21G Y 209
3-21G Y 165 CC13N CINCClz DZ Y 257
DZ Y 218 CFHzN HCN HF ... 4-31G Y 128
DZ FC 217 CH3NOZ C 0z... NH, DZ Y 258
4-31G. EFV I 219 CHZNZ HzNCN 4-31G, 4-31G* Y, 1 259
3-21G Y 165 CHzNz HZNNC 4-31G, 4-31G* Y, 1 259
DZ Y 220 CHzCO3 HZC03 4-31G Y 260
min Y 221 CLizOz LizCOz 3-21G Y 209
ext FC 222 CNa2OZ NazCOz 3-21G Y 209
STOBG, 4-31G FC 54 CHOc HCOc 4-31G Y 260
4-21G FC, I 11 F6P PF5 3-21G, 3-21G* Y 189
STO3G I 223 F6P PF6 DZ Y 261
HF limit FC 224 F4Si SiF4 3-21G Y 165
4-31G* Y 225 F3H3 DZ+P, CI Y 216
DZ I 226 F,HSi HSiF3 3-21G Y 165
ST03G, 3-21G, Y 183 FzHzSi HzSiFz 3-21G Y 165
4-21G, 6-21G FH30 Hz0...HF 6-31G Y 262
STOIG, DZ I 213 FH,O HzO HF... TZ+P Y 263
6-31G*, MP2 Y 122, 138 FH30 HZO HF... CSID Y 264
3-21G, 6-31G* Y 136 FH3Si SiH3F 3-21G Y 192
DZ+P I 49 FH3Si SiH3F 3-21G Y 165
6-31G** Y 227 H9+ H*+ CISD Y 178
CISD Y 57, 228 H7+ H,+ CISD Y 178
CI Y 229 H5+ HE.+ CISD Y 178
SCEP,CEPA Y, 1 230 H6P PH5 CEPA FC 233
est Y, 1 231 H4Nt NH4+ 6-31G** Y, 1 75
CISD Y 232 H,N+ NH4+ 6-31G*, MP2 Y 138
DZ+P Y 168 H4N+ NH4+ CISD Y 139
6-31G*, MP2 Y 138 H4NZ HzNNHz STOBG, 4-31G, Y 265
STOIG, 4-31G FC 54 4-31G*, 6-31G*, CI
STOBG, 3-21G, Y 191 H4°Z HZNNHZ 6-31G*, MP2 Y 122,138
4-31G, 6-21G H40Z (HzO)z 4-31G, 6-31G* Y 266
3-21G, 3-21G* v 189 H4°Z (Hz0)~ CI Y 267
CEPA FC 233 H4°Z (Hz0)z 4-31G FC, I 268
ST03G, DZ I 213 H4OZ (HzO)z 4-31G I 269
DZ+P Y 234 HiOz (HzO)z DZ+P Y, I 270
6-31G*, Mp2 Y 138 H4°Z 4-31G u,I 271
3-21G, 6-31G* Y 190 H4°Z (H@)z 4-31G Y 272
722 Chemical Revlews, 1988, Vol. 88, No. 4 Hess et al.

TABLE IV (Continued)
structure type of structure type of
formula or name calcn" typeb ref formula or name calcna typeb ref
H4O2Li+ (H20)2Li+ 4-31G FC, I 268 H4Si2 disilene DZ, DZ+P U 275
H,O2Siz (H2Si0)2 3-21G U 273 H3N3 triaziridine 6-31G*, MP2 u, I 276
HIP+ H,P+ 6-31G*, MP2 u 138 H3N3 triazine 6-31G*, MP2 u, I 276
H4SzSiz (HzSiS)z 3-21G U 273 H3N0 HONHz 4-31G u, I 277
H,Si SiH, ST03G, 4-31G FC 54 H,NO HONHz 6-31G*, MP2 U 122, 138
H,Si SiH, 6-31G*, MP2 u 138 H3N0 HONHz DZ FC 240
H,Si SiH4 3-21G, 3-21G* u 189 H3N0 HONHz STOSG, 4-31G V, I 278
H4Si SiH4 3-21G, 6-31G* u 190 4-31G
H4Si SiH, DZ, DZ+P U 274 H2N20 HzN=NO 4-31G u, I 279
H4Si SiH, 6-31G** u, I 75 H2N20 HN=NOH 4-31G u, I 279
H,Si SiH, 3-21G Y 165 HzO, (HOz)z DZ+P U 197
"DZ means generally a true double-zeta basis set. It may also mean a valence-shell DZ set or a medium-sized basis set of a quality
somewhat better than DZ. u:frequencies computed. FC: force constants reported only. I: intensities comDuted (IR and/or Raman).


- I. I. .I.

I I . I . . ..I I I .

I I1 1,
I600 3200 2800 2400 2000 1600 1200 800 400
I I I (( I I 1 I I
3600 3200 2800 2000 1600 1200 800 400
Figure 12. Comparison of computed IR spectralo3of I1.1.11- cm"
propellane with that of experiment.lo2
Figure 13. Comparison of computed IR s ectralM of methyle-
necyclopropene with that of experiment. 18
sponding 13Cz-cyclobutadienemixture. The observed
and computed spectra are in good agreement. In the
computed spectrumz5there are six bands below 1700 and co-workers were able to assign the fundamentals
cm-' of relative intensity greater than 0.01. Michl et in the IR and Raman spectra.
al. observed six bands in this region which correspond
well with those computed. A t high frequency a broad D. Methylenecyclopropene
band is observed at 3049 cm-'. calculation^^^ predict
five weak C-H stretches within an 18-cm-' region and The recent synthesis of methylenecyclopropene
a sixth of very weak intensity at somewhat higher fre- (IX)'04J05was confirmed in part by its IR spectrum.lo4
quency. Billups reported five bands which he assigned to the
spectrum of IX. However, while the computed spec-
C. [1.1.1]Propellane
Wiberg and Walker reported in 1982 the synthesis
and IR spectrum of the highly strained but remarkably
stable hydrocarbon [l.l.l]propellane (VIII).102 An

trum (6-31G*)" agreed very well with four of the bands

reported (Figure 13), the relatively intense band at 904
cm-' (not shown in the figure) did not appear to cor-
relate with any of the computed frequencies. While
several bands were computed to lie in this region (taking
Vlll into account the fact that computed bands usually ap-
pear at higher frequency than experiment), all were
unusual aspect of the IR spectra of VI11 is a very intense computed to be of quite low intensity. Billups subse-
band at 612 cm-l which appears to be characteristic of quently informed us that the band at 904 cm-l is in fact
highly strained cyclopropanes.lo2 Wiberg, Dailey, and not due to IX, This was further confirmed by Maier
Walker carried out a vibrational calculationlo3(6-31G*) and collaboratorslo7in an independent synthesis of IX
of frequencies and IR intensities. It is seen from Figure in which they found no absorption in the 900 cm-l re-
12 that not only is there predicted a very intense band gion due to IX. Billupslo8has since located additional
at low frequency but the overall experimental pattern bands in the experimental spectrum and these along
is reasonably well reproduced by the calculated spec- with 6-31G*/MP2 computed f r e q u e n c i e ~are~ ~ also
trum. With the aid of the computed spectrum Wiberg given in Figure 13.
Calculatlons of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 723

I 1 I I I I I I I I

4-31 G
I I. I I.

I I.. I

I. I.
.I ClSD I .I

3600 2800 11 2000

1600 1200 800
Figure 14. Comparison of c o m p ~ t e d 'IR
~ spectra of cyclo- 11 I 1 I I I I I I
propenylidene with that of experiment." 3600 3200 2800 2400 2000 1600 1200 800 400

E. Cyclopropenylldene Figure 15. Comparison of computed IR spectra of thiirene with

that of experiment."' Open bars give estimated uncertainty of
experimental intensities, i.e., experimental intensity is estimated
Computed spectra are not only of use in identifying to lie somewhere within the open bar.
unstable molecules but also in aiding in the charac-
terization of reactive intermediates. The recent syn-
thesis of the singlet carbene cyclopropenylidene (X)

and the confirmation of this synthesis by comparison

of experimental and computed IR spectra provides a
nice example of this. Lee, Bunge, and SchaefeP have
carried out an SCF computation of the IR spectrum
with a double zeta plus polarization basis. The result
compared very favorably with the matrix spectrum
observed by Maier's group (Figure 14).lO9 Schaefer and Figure 16. Calculated a b initio spectra of tetrahedrane.l14
collaborators have also calculated the spectrum of the
lowest triplet state (3B1)of X. This does not compare
as well as with the experimental spectrum of X as does
the calculated spectrum of the lower energy singlet (lA1) this ring deformation should occur most likely below
ground state. Hence the synthesis of X was confirmed 400 cm-l.'13 However, it was subsequently shown that
by ab initio results, and its electronic state is identified this prediction is likely to be wrong since when the
as 'Al. spectrum was calculated with a better basis set (6-
31G*)82the Al ring deformation is computed to be at
F. Thllrene a significantly higher frequency than with the 4-31G
basis set. In fact with the 6-31G* basis set it is calcu-
Thiirene (XI), like cyclobutadiene, is a Hiickel 4n lated to be at slightly higher frequency than found by
system and is potentially antiaromatic.l1° Its synthesis Strausz (see Figure 151, but still at slightly lower fre-
quency (711 cm-') than the more intense C-H bend at


in a matrix was reported independently by two groups

717 cm-l. Subsequently the vibrational spectrum was
recomputed with inclusion of correlation (DZF'-CISD):2
and these results are also shown in Figure 15. It is
apparent that the original assignment of the C-S stretch
by Strausz is correct since this best calculation places
it at 723 cm-' which is 123 cm-l higher in frequency
in 19773 and 1978.'11 Both obtained the thiirene than the more intense C-H bend, and in agreement
spectrum which was found to agree reasonably well with with Strausz's original assignment. This unexpected
a computed 4-31G spectrum.l12 However, Strausz as- shift in computed frequenciesserves as a useful warning
signed a band of medium intensity at 657 cm-' to the against implicit trust in the theoretical results.
Al symmetric ring deformation. This is at a higher
frequency than the corresponding 4-31G computed V I . Some Predictions of I R Spectra of
band (509 cm-l). Normally frequencies computed with Unknown Molecuies
a double zeta or larger basis set are computed to be of
too high frequency. Hence it was suggested that the The IR spectra of two interesting but unknown
original assignment by Strausz was incorrect and that molecules on the C4H4 potential surface have recently
724 Chemical Reviews, 1986, Voi. 86, No. 4 Hess et al.

TABLE V. Vibrational Calculations of Organic Systems

structure type of structure type of
formula or name calcn" typeb ref formula or name calcn" typeb ref
CFo CF, 6-31G* U 280 CH,F,OP CH-POF, 3-21G Y, I 313
CF) CF) 6-31G* Y 280 C H "~ CHEI DZ+P FC, I 306
CFz++ CFz++ 6-31G* Y 280 CH~N H$=NH ext Y 314
CF4 CF4 3-21G Y 136 CH3N HzC=NH 6-31G* Y 138
CF30 CF30 3-21G Y, 1 281 CH3N HzC=NH 6-31G*, MP2 Y 122, 133
CF30- CF30- 3-21G u, 1 281 CH3NO HCONHZ 4-31G Y, I 315
CF30Z CF300 3-21G u, 1 282 CH3NO HCONHp 4-31G* v 316
CHCl3 CHCl3 ST04G I 283 CH3NO HCONHp 4-31G Y, I 317
CHF3 CHF3 4-31G Y 284 CH3NO CH3NO 4-31G v, I 318
CHF3 CHF3 3-21G Y 136 CH3N0 HzC=NOH STOBG, 4-31G Y 319,320
CHO HCO min Y 285 CH3N02 CHBNOz 3-21G, 6-31G* Y 291
CHO+ HCO+ 6-31G** Y, 1 132 CH30+ HzCOH+ 6-31G*, MP2 Y 138
CHO+ HOC+ 6-31G** u, 1 132 CH30 CH30 3-21G, 6-31G* Y 321
CHO+ HCO+ CI Y 287 CH30 CH30 DZ, CASSCF Y 322
CHOZ- HCOc STOIG, 4-31G Y 288 CH30 CH30 DZ Y 323
CHZ CHZ CISD Y 33 CH30 CHzOH 3-21G, 6-31G* Y 321
CHz+ CHz+ 6-31G*, MP2 Y 138 CH3S+ CH3S+ 3-21G Y 324
CHz+ CHz+ STO3G Y 120 CH3S+ CHZSH' 3-21G Y 324
CHzFz CHZFZ 4-31G Y 284 CH4 CH4 DZ+P FC, I 325
CHzFz CHzFz 6-31G*, MP2 Y 133 CHI CH4 DZ+P I 46,49
CHzN HZCN GVB-CI Y 289 CH4 CH4 6-31G** Y, 1 75
CHzN HCNH GVB-CI Y 289 CH4 CH4 6-31G*, MP2 V 122, 133,
CHzNz CHz=Nz STO3G FC 290 138
CHZNZ HzNCN 6-31G* Y 291 CH4 CH4 STOBG, 4-31G FC 54
CHZNOZ CHZNOZ 3-21G, 6-31G' Y 292 CHI CH4 CEPA FC 326
CHZO HzC=O DZ, CI Y 293 CHI CH4 4-31G Y 58
CHzO HZC-0 4-31G Y, 1 66 CHI CH4 4-21G Y, 1 11
CHzO H&=O DZ+P Y 294 CH4 CH4 CISD Y 139
CHzO HzC=O ext Y, 1 41, 63 CHI CHI CI Y 304
CHzO HzC=O MCSCF, CI Y 295 CH4 CH, 3-21G, 6-31G* V 136
CHZO H&=O DZ Y, 1 296 CHI CHI 4-31G I 327
CHzO H&=O 6-31G*, MP2 v, 1 122, 133 CH4F+ H3CFH' 6-31G*, MP2 Y 138
CHzO HZC=O 6-31G* Y 138 CH4N+ HZCNHz+ 6-31G*, MP2 Y 138
CHZO H2C-O CI, CEPA Y 241 CH40 CH3OH min FC 328
CHzO H&=O ST03G Y 297 CH40 CHBOH 4-31G Y 180,329
CHzO H&=O 3-21G, 6-31G* Y 136 CH40 CH3OH 3-21G, 6-31G* Y 136,321
CHzO H&=O DZ, DZ+P, CI Y 298 CH40 CH30H DZ FC 240
CHzO H2C-O STOBG, 4-31G Y 185 CH40 CHaOH 6-31G*, MP2 Y 122, 133
CHzO HOCH DZ+P Y 294 CH40 CH3OH 6-31G* Y 138
CHzO HOCH ST03G Y 297 CH402 CHz(0H)z STOBG, 4-31G Y 185
CH20+ HCzO+ 6-31G*, MP2 Y 138 CH4S CH3SH 4-31G Y 329
CH202 HCOOH 6-31G FC 299 CH4S CHSSH 3-21G*, 6-31G* Y 189
CHzOz HCOOH 3-21G Y 136 CH4S+ CHzSHz+ 3-21G Y 324
CHzOz HCOOH DZ, 4-31G Y 300 CH4Si HzSi=CH2 4-31G Y 330
CH202 HCOOH STOBG, DZ Y 301 CHS+ CH5+ 6-31G*, MP2 Y 138
CHzOz HCOOH 6-31G*, MP2 Y 133 CHSN CH3NHz 4-31G Y 329
CHZ03 HCOOOH 4-31G Y 13 CHSN CH3NHz 6-31G* Y 138
CHzOS HCOSH 4-31G Y 302 CHSN CH3NHz 3-21G, 6-31G* Y 136
CHzS H&=S CI, CEPA Y 241 CHSN CH3NHz 6-31G*, MP2 Y 122, 133
CHzS H2C-S 3-21G*, 6-31G* Y 189 CHeN CH3NHz STOBG, 4-31G, Y, 1 331
CHzS HzC=S DZ+P I, 303 4-31G*
CH3 CH3 CI Y 304 CH50+ H3COHZ' 6-31G*, MP2 Y 138
CH3 CH3 DZ+P, CEPA u, 1 305 CHsN+ H3CNH3' 6-31G*, MP2 Y 138
CH3+ CH3+ 6-31G*, MP2 Y 138 CHsSi CH3SiH3 DZ,DZ+P Y 274
CH3Br CH3Br DZ+P FC, I 306 CHBBZ methyldiborane 4-21G Y 332
CH3Cl CH&l 4-31G 0 307 CZH HCC CISD, 6-31G** Y 333
CH3Cl CHaCl 6-31G*, MP2 Y 133 CZH" CzH+ 6-31G*, MP2 Y 138
CH3Cl CH&l 3-21G*, 6-31G* Y 190 CZH- HCC- CEPA, ext Y 194
CH&l CH&I 4-31G, 6-31G* FC, I 308 C2HCl+ HCCCP DZ+P Y 334
CH&l CH3Cl 3-21G, 6-31G* Y 309 CzHCl HCCCl DZ+P Y 335
CH3Cl CH3Cl DZ+P FC, I 306 CzHCl HCCCl DZ+P, CEPA Y 134
CH3CI CH&l DZ+P, 6-311G**, Y 310 CzHF FCCH DZ+P Y 335
MP2 CZHF FCCH 3-21G Y 136
CH&lMg CHaMgCl 3-21G, 6-31G* Y 309 CzHF FCCH DZ+P. CEPA Y 134
CH3F CH3F 4-31G Y 284, 307 CzHN HCCN 6-31G,'6-31G*, MP2 Y 336
CH3F CHaF DZ+P F C , I 306 CzH2 HCCH DZ Y 63
CHSF CH3F 4-31G, 6-31G* FC, I 308 CZHZ HCCH 6-31G*, MP2 Y 122, 133
CHaF CH3F DZ+P FC, I 311 CzHz HCCH 6-31G* Y 138
CH3F CHsF 3-21G, 6-31G* Y 136 CzH2 HCCH 4-31G I 327
CH3F CH3F 6-31G*, MP2 Y 122, 133 CzHz HCCH 6-31G** Y, 1 75
CHsF CH3F 6-31G* Y 138 CzH2 HCCH DZ+P, CI FC 337
CH3F CHBF DZ+P, 6-311G**, Y 310 C A HCCH TZ+P, CI Y 338
MP2 CiH, HCCH DZ+P Y 335
CH3F CH3F DZ+P FC 312 CZHZ HCCH ext Y, 1 339
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 725

TABLE V (Continued)
structure type of structure type of
formula or name calcn" typeb ref formula or name calcna typeb ref
HCCH 3-21G,6-31G* Y 136 CzH& HOCHSHqOH DZ Y 355
HCCH DZ+P Y, I 340 C,HnS+ 3-21G Y 324
HCCH DZ+P, CEPA 134 CH;SCH3+- 3-21G Y 324
H&=C CISD 341 HCCCO+ 3-21G, 6-31G* Y 356
HFC=CFH 3-21G 136 HCCCP DZ+P Y 142
HzNCN 6-31G* 291 cyclopropenylidene DZ, DZ+P Y 78
oxirene 3-21G 113 DZ+P
glyoxal DZ 68 HCCCHO CI/DZ+P Y 351
glyoxal 4-31G 66 cyclopropenyl rad. MCSCFI3-21G Y 358
thiirene 4-31G 112 cyclopropene 4-31G Y 58
thiirene 3-21G 113 cyclopropene 6-31G** Y, I 16
vinyl 6-31G**, GVB 343 cyclopropene 6-31G*, MP2 Y, I I9
CHZ=CH+ 6-31G*, MP2 138 cyclopropene DZ+P Y, I 18
H,C=CHF 3-21G 345 CHzCCHz 3-21G Y 136
HZNCCH 6-31G* 291 CHzCCHz 6-31G* Y 291
CH3CN 3-21G 136 CH3CCH 3-21G Y 136
CHaCN 4-31G* 346 CHSCCH 6-31G* Y 291
CH3CN 6-31G* 291 HCCCHzNH2 4-31G(N*) Y, I 359, 360
CH3NC 3-21G 136 CHZ=CHCHO DZ, 4-31G Y 69
azirene 3-21G 113 CHz=CHCHO 3-21G Y 136
HzC=CH2 3-21G, 6-31G* 136 CH,=CHCHO 4-31G Y, I 66
H&=CH2 DZ 63,342 malonaldehyde DZ+P Y 361
HZC=CH2 6-31G*, MP2 30, 122, CHZ=CHCH, 3-21G/ v 362
133 MCHF
HZC=CH2 6-31G* 138 cyclopropyl radical 4-31G Y 363
H2C=CH2 4-31G 327 CHSCHZCN 3-21G Y 136
HZC=CHz 6-31G** 15 CH3CH=CH2 4-31G Y 60
H2C=CH2 DZ+P 194 CH&H=CHz 3-21G, MCHF Y 362
H2C=CH2 ext 339 cyclopropane 4-31G Y 58, 59,
HZC=CH2 4-31G 64,66 363
HZC=CH2 ST04G 98 cyclopropane 3-21G Y 136
H2C=CHp DZ+P 40 cyclopropane ST03G, 4-31G, Y 81
H2C=CH2 ST03G, 6-31G* 106 6-31G**
H2CUH2 3-21G 345 CHzCHzCHz MCSCF/DZ Y 364
2,4-diboramethyl- DZ 347 CH2CH2CHZ DZ Y 365
enecyclopropane CHaCHZCHO 4-21G Y, I 366
CH3CHF 3-21G 345 oxetane 4-21G Y, I 361
oxirane ST03G, 4-31G, 81 acetone 3-21G Y 136
6-31G** epoxypropane 6-31G* Y, I 368
oxirane 6-31G* 13 epoxypropane 4-31G Y, I 12
oxirane 4-31G 12 methylthirane 6-31G Y, I 369
oxirane 3-21G 136 CH3CONHCH3 4-31G Y 370
CHBCHO 4-31G, 6-31G** 348 CHSCONHCH3 ST03G, I 371
CHSCHO 3-21G 136 3-21G
HCOOCHI 3-21G 136 CHSCH2CHs 4-31G Y 58,59
CH3COOH 3-21G 136 CH,CH?CH, 6-31G*, MP2 Y 133
(HzC0)z 3-21G 213 CH~=SI(CH~)~ 4-31G v, I 372
(HCOOH)2 ST03G, DZ 301 (HzC=NOH)S ST03G Y 320
H2C=CHSH 4-31G 349 tetralithio- STOIG, 4-31G/ Y 373
thiirane 6-31G* 82 tetrahedrane 5-21G(Li)
CH3CH2 3-21G 345 HCCCCH DZ+P Y, I 374
CH3CH2 4-21G 350 HCCCCH 3-21G Y 136
CH3CH2' 6-31G*, MP2 138 cyclobutadiene ST04G Y, I 98, 100
CH3CH2F 3-21G 136 cyclobutadiene 6-31G*, MP2 Y, I 25
aziridine STOIG, 4-31G, 81 cyclobutadiene DZ+P Y, I 95
6-31G* tetrahedrane 6-31G*, MP2 u,I 114
aziridine 3-21G, 6-31G** 136 bicyclobutene 6-31G*, MP2 u,I 115
CH,CH=NH DZ 351 methylenecyclopropene 6-31G* Y, I 106
CH,CN=CHZ DZ 351 methylenecyclopropene 6-31G*, MP2 Y I9
HCONHCHa 4-31G, 4-31G* 352 cyclobutyne DZ, DZ+P Y 315
CHSCH3 DZ 63 uracil STO3G Y 316
CHSCH, 4-31G 353 uracil 4-31G Y, I 311
CH3CH3 4-31G 58, 59, CH&CCHO DZ Y 351
354 1,3-butadiene 4-31G Y 318
3-21G 59 1,3-butadiene DZ+P Y 319
6-31G*, MP2 122 1,3-butadiene 4-31G Y, I 66
6-31G* 138 1,3-butadiene 3-21G Y 136
4-31G 321 CH3CCCHB 3-21G Y 136
6-31G** 15 cyclobutane 4-21G Y, I 380
(HsC=NOH), STO3G 320 butane 6-31G Y 381
CHaOCH, 4-31G 65 lithium DZ, DZ+P FC 382
3-21G Y 136 cyclopentadienide
6-31G*, MP2 Y 133 C5H5N pyridine 4-31G Y, I 383
726 Chemical Reviews, 1986, Voi. 86, No. 4 Hess et al.

TABLE V (Continued)
structure type of structure type of
formula or name calcna typeb ref formula or name calcn" typeb ref
C5H5N pyridine 4-21G Y, I 384 CsH, benzene 4-21G u, I 67
C5H5N,0 guanine STO3G Y 385 C6H5 triprismane 4-21G u, I 388
C6H5 [ l.l.l]propellane 6-31G* u,I 103 C8H8 cubane DZ Y 389
C5H,0 CH2=CHCOCH=CH2 4-31G FC 386 CsH8 cubane DZ Y, I 390
C5N30- (NC)2C=C(CN)O- ST03G Y 387 CloH8 naphthalene 4-21G Y, I 391
CBN4 (NC)&=C(CN)Z STO3G Y 387 C,H, polyacetylene ST03G, 4-31G Y 392
"DZ means generally a true double-zeta basis set. It may also mean a valence-shell DZ set or a medium-sized basis set of a quality
somewhat better than DZ. *Y: frequencies computed. FC: force constants reported only. I: intensities computed (IR and/or Raman).

phistication of the calculation. This accuracy, of course,

can hardly compete with high-resolution experiments.
Finer details of a theoretical spectrum must not be
trusted, but the overall pattern is usually remarkably
accurate and can aid in the identification of new species
and in the interpretation of their experimental spectra.

I l I II I I
AiBz BzAiAqB,BzAiB, By Ai
(1) Parr, R. G. Quantum Theory of Molecular Electronic
Structurs; Ben'amin: New York, 1963.
(2) Zahradnik, R. hortschr. Chem. Forsch. 1968, 10, 1.
(3) Krantz, A.; Laureni, J. J. Am. Chem. SOC.1977, 99, 4842;
cm 1981,103, 486.
(4) Schutte, C. J. H. Structure and Bonding (Berlin) 1971, 9,
Figure 17. Calculated ab initio spectra of bicy~lobutene."~ 213.
(5) Fredkin, D. R.; Komornicki, A.; White, S. R.; Wilson, K. R.
J. Chem. Phys. 1983, 78, 7077.
(6) Schrader, B.; Bou eard, D.; Niggemann, W. In Computa-
been ~ a l c u l a t e d . ' ~ ~Tetrahedrane
J~~ (XII) and bi- tbonal Methods in themistry; Bargon, J., Ed.; Plenum: New
cyclobutene (XIII) are both of synthetic interest; the York, 1980.
(7) Fogarasi, G.; Pulay, P. Ann. Reu. Phys. Chem. 1984,35,191;
In Vibrational Spectra and Structure; Durig, J. P., Ed.; El-

sevier: Amsterdam, 1985, Vol. 14.
(8) Born, M.; Oppenheimer, R. Ann. Phys. (Leipzig) 1927, 84,
(9) Wilson, E. B., Jr.; Decius, J. C.; Cross, P. C. Molecular Vi-
brations; McGraw-Hill: New York, 1955.
XI1 Xlll (10) Mills, I. M. In Molecular Spectroscopy: Modern Research;
Rao, K. N., Mathews, C. W., Eds.; Academic Press: New
York, 1972.
former because of its unique structure and the latter Pulay, P.; Fogarasi, G.; Pang, F.; Boggs, J. E. J. Am. Chem.
because of its unusual predicted geometry. Hehre and SOC.1979, 101, 2550.
Pople1l6found that XIII is computed (STO-3G) to have Hoy, A. R.; Mills, I. M.; Strey, G. Mol. Phys. 1972,24, 1265.
Bock, C. W.; Trachtman, M.; George, P. J. Mol. Spectrosc.
a puckered structure rather than the expected planar 1980, 84, 256.
one. This was given further support when the same Hennig, P.; Kraemer, W. P.; Diercksen, G. H. F.; Strey, G.
result was obtained for XI11 with the larger 4-31G basis Theor. Chim. Acta 1978, 47, 233.
Botschwina, P., unpublished results, 1981.
set.'17 It is hoped that these computed spectra (Figures Meyer, W. In Modern Theoretical Chemistry; Schaefer, H.
16 and 17) will be of eventual use in the identification F., 111, Ed.; Plenum: New York, 1977; Vol. 3.
Sexton, G. J.; Handy, N. C. Mol. Phys. 1984,51, 1321.
of XI1 and XIII. Kraemer. W. P.: Roos. B. 0.; . Sierrbahn.
- P. E. M. Chem. Phys.
1982, 69,'305. '

(19) Richards, W. G.; Horsley, J. A. Ab Initio Molecular Orbital

V I I . Compilation of ab Initio Vibrational Calculations for Chemmts; Clarendon: Oxford, 1970.
(20) Schaefer, H. F., 111. The Electronic Structure of Rigorous
Calculations Quantum Mechanical Results; Addison-Wesley: Reading,
Massachusetts, 1972.
A compilation of ab initio vibrational calculations of (21) Cook, D. B. Ab Initio Valence Calculations in Chemistry;
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