Journal of Molecular Structure: THEOCHEM 897 (2009) 3235

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Journal of Molecular Structure: THEOCHEM

journal homepage: www.elsevier.com/locate/theochem

DFT and TDDFT study of carbon trioxide

Changyong Qin *, Tsz-Yan Soo
Department of Chemistry, Vassar College, Box 748, 124 Raymond Avenue, Poughkeepsie, NY 12604, USA

a r t i c l e i n f o a b s t r a c t

Article history: Carbon trioxide has been studied using DFT and TDDFT methods with different combinations of GGA
Received 10 July 2008 functionals and correlation consistent basis sets. The C2v isomer is calculated to be 2.5 kcal mol1 and
Received in revised form 4 November 2008 12.5 kcal mol1 lower in energy than D3h with a conversion energy barrier of 5.0 kcal mol1 and
Accepted 19 November 2008
12.9 kcal mol1 by PW91PW91 and B3LYP, respectively. All of the above include zero-point energy cor-
Available online 3 December 2008
rections. The geometry changes almost linearly along the reaction coordinate and the TS structure is
approximately an average of D3h and C2v with an imaginary OCO bending mode of 421i cm1. However,
Keywords:
D3h is more favored in low energy excited singlet states. These states also promote the C2v ? D3h
Carbon trioxide
Ground state
conversion.
Excited state 2008 Elsevier B.V. All rights reserved.
Density functional theory
Time-dependent DFT

1. Introduction 2. Theory and method

Carbon trioxide has been well characterized both experimen-
tally [14] and theoretically [38] because of its importance in
atmospheric and astronomic chemistry. Initially, three isomeric
structures were considered, chain-type Cs, cyclic C2v and resonant
D3h [9], but early vibrational spectra pointed to a low-symmetry
structure, Cs or C2v. Consequently, extended Hckel calculations
excluded the Cs isomer because of its signicantly higher energy
than the other two structures [5]. However, the D3h isomer was cal-
culated to be only 0.1 kcal mol1 higher in energy than the C2v at
the MRCI+Q(16,13)/6-311+G(3df) level [7]. If an equilibrium could
be assumed between C2v and D3h and the contribution from entro-
py to free energy could be neglected, a halfhalf mixture of C2v and
D3h would be expected.
Eventually, the D3h structure was identied by Kaiser and co-
workers in CO2 ice using low-temperature matrix isolation and
spectroscopy techniques [3]. Thermodynamically, co-existence of
the two isomers under low temperature (195 K, dry ice) implies
that they are very close in energy with C2v slightly favored. A re-
cent study by Kowalczyk and Krylov shows that the energy differ-
ence is about 3.0 kcal mol1 and that the vibrational coupling with
low-lying electronic excited states should be considered in deter-
mining the CO3 potential energy surface [8]. In this paper, a Den-
sity Functional Theory (DFT) study on CO3 has been reported,
including both its ground and excited state potential energy sur-
faces (PES).
* Corresponding author. Tel.: +1 845 437 5736; fax: +1 845 437 5732.
E-mail addresses: chqin@vassar.edu, cyqin@hotmail.com (C. Qin).
The ground-state geometries of CO3 were optimized using DFT
methods with generalized gradient approximation (GGA) for the
exchange-correlation potential. Hybrid functionals, B3LYP [10,11]
and PW91PW91 [1214], were used in combination with Dun-
nings correlation consistent basis sets [1518] (aug-cc-pVDZ,
aug-cc-pVTZ and aug-cc-pVQZ). All calculations were performed
using the Gaussian03 suite of programs [19]. Second derivatives
computed from nite differences of the analytic rst derivatives
were used to calculate harmonic frequencies and to judge a sta-
tionary point as a minimum or a transition state. The intrinsic reac-
tion coordinate (IRC) [20,21] was followed in both directions from
the transition state to verify the connection between D3h and C2v
on the ground state PES (shown in Scheme 1). Excited states were
also examined using Time-Dependent DFT.
3. Results and discussion
3.1. Ground state isomers of CO3
Structures for two isomers are optimized using B3LYP and
PW91PW91 correlation-exchange functionals in combination with
Dunnings correlation consistent basis sets and results are listed in
Table 1. It is found that all bond lengths increase from B3LYP to
PW91PW91 by 0.0100.020 , but this dependency is negligible
and they all agree well with the CCSD(T)/cc-pVTZ geometry in
Ref. [8]. As for basis set, aug-cc-pVDZ gives longer bond distances
than aug-cc-pVTZ and aug-cc-pVQZ by 0.0060.011 , while a con-
sistency was observed between the latter two in both the geometry

0166-1280/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.theochem.2008.11.018
 C. Qin, T.-Y. Soo / Journal of Molecular Structure: THEOCHEM 897 (2009) 3235 33

O2 Selected eigenvalues and molecular orbitals are displayed in Fig. 1.

O2 O2 From D3h to C2v, all degenerate orbitals are split into bonding and
C1 anti-bonding orbitals between O3 and O4. For example, B1
C1 C1 (HOMO-2) and A1 (HOMO-3) promote bonding character between
O3 and O4 and stabilize the C2v structure, while A2 (HOMO) and B2
O4 O3 O4 O3 O4 O3 (HOMO-1) have anti-bonding components and destabilize the O3
D3h TS C2v O4 bond. However, all those orbitals are fully lled and their effects

Scheme 1.

and energy. Therefore, only the PW91PW91/aug-cc-pVQZ results 0.00

A1'
will be discussed in detail. From D3h to C2v, C1O2 is shortened from A1

1.258 to 1.179 while C1O3 and C1O4 are elongated to 1.342 -.05
A2"
B1
and the O3C1O4 bond angle decreases from 120 to 73. Corre-
L+1
spondingly, the C1O2 stretching frequency increases from L+1
1508 cm1 to 2002 cm1. On the other hand, the atomic polar ten- -.10
sor (APT) [22] charge of C1 increases by 0.80 e and 0.46 e for O2,
while only 0.17 e for O3 and O4 (Table 1). The same trend was de- -.15
tected at the B3LYP/aug-cc-pVQZ level. Since Mulliken charges
show large variations with respect to the basis set, only the APT

Eigenvalue (hartrees)
values are discussed. The calculated frequencies by B3LYP and -.20 B2
PW91PW91 agree within 5%. For C2v, they also agree well with L

the experimental results in Ref. [3], but both B3LYP and -.25
PW91PW91 did not provide a good estimation for either of the
two E0 modes of D3h. For example, the E0 CO stretching mode is cal-
culated to be 1508 cm1, which is about 25% higher than an IR va- -.30 A2
A2' L
H B2
lue of 1165 cm1 [3], indicative of the importance in including the
vibronic coupling and anharmonic correction [8]. -.35 H-1
E"
H H-1
The D3h isomer is calculated to be 2.5 kcal mol1 and B1
E'
12.5 kcal mol1 higher in energy than its C2v analogue by H-2

PW91PW91 and B3LYP, respectively (Table 1). In addition, the rel- -.40
H-2 H-3
ative Gibbs free energy at 298.15 K is slightly increased to
2.9 kcal mol1 and 12.8 kcal mol1, respectively. Experimentally, -.45 H-3
A1

two isomers were co-identied under low temperature (195 K, B2

H-4
dry ice) [3]. Therefore, they must be very close in energy or the po- A1 H-4
A2"
-.50
tential energy surface along D3h and C2v must be very at. Our cal- B1 E'
H-5
culated PW91PW91 value is only 0.5 kcal mol1 smaller than that
H-6 H-5 H-6
by Kowalczyk et al. at the CCSD(T)/aug-cc-pVQZ level [8], but sig- -.55
nicantly larger than 0.1 kcal mol1 predicted by MRCI+Q(16,13)/
6-311+G(3df) [7]. Based on the above two views, the gas phase Fig. 1. Selected molecular orbitals of CO3 (Left: C2v; right: D3h; red: unoccupied;
CO3 is better described by PW91PW91, which is encouraging since blue: occupied; H: HOMO; L: LUMO) (For interpretation of the references to colour
in this gure legend, the reader is referred to the web version of this article).
PW91PW91 will also be used for the CO3/Ag system in the future.

Table 1
Relative energies, free energies, bond lengths, angles and charges of CO3.

Method Basis seta G298kb

rel Erelb aO  C1 O4
3
Bond length Mulliken charge APT charge
kcal/mol kcal/mol degree (C1O2, C1O3, O3O4) e (C1, O2, O3) e (C1, O2, O3)
D3h Isomer
cc-pVDZ 11.0 10.7 120.0 1.254, 1.254, 2.171 +0.81, 0.27, 0.27 +0.30, 0.10, 0.10
B3LYP cc-pVTZ 12.9 12.7 120.0 1.248, 1.248, 2.162 +0.69, 0.23, 0.23 +0.27, 0.09, 0.09
cc-pVQZ 12.8 12.5 120.0 1.246, 1.246, 2.158 +1.03, 0.34, 0.34 +0.30, 0.10, 0.10
cc-pVDZ 1.1 0.7 120.0 1.266, 1.266, 2.193 +0.87, 0.29, 0.29 +0.42, 0.14, 0.14
PW91PW91 cc-pVTZ 3.1 2.7 120.0 1.260, 1.260, 2.182 +0.63, 0.21, 0.21 +0.39, 0.13, 0.13
cc-pVQZ 2.9 2.5 120.0 1.258, 1.258, 2.180 +0.84, 0.28, 0.28 +0.39, 0.13, 0.13
C2v Isomer
cc-pVDZ 0.0 0.0 72.7 1.178, 1.338, 1.587 +0.75, 0.25, 0.25 +1.24, 0.62, 0.31
B3LYP cc-pVTZ 0.0 0.0 72.7 1.170, 1.332, 1.579 +0.58, 0.28, 0.15 +1.26, 0.62, 0.32
cc-pVQZ 0.0 0.0 72.8 1.169, 1.330, 1.579 +1.11, 0.47, 0.32 +1.26, 0.62, 0.32
cc-pVDZ 0.0 0.0 73.1 1.189, 1.350, 1.607 +0.77, 0.27, 0.25 +1.18, 0.58, 0.30
PW91PW91 cc-pVTZ 0.0 0.0 73.0 1.180, 1.344, 1.598 +0.48, 0.24, 0.12 +1.19, 0.59, 0.30
cc-pVQZ 0.0 0.0 73.0 1.179, 1.342, 1.597 +0.90, 0.38, 0.26 +1.19, 0.59, 0.30
C2v Transition state
B3LYP cc-pVQZ 12.9 12.9 104.1 1.220, 1.264, 1.994 +1.05, 0.39, 0.33 +0.32, 0.24, 0.04
PW91PW91 cc-pVQZ 5.0 5.0 93.2 1.215, 1.291, 1.876 +0.86, 0.34, 0.26 +0.44, 0.30, 0.07
a
All are augmented with diffuse functions.
b
The zero-point energy correction is included.
34 C. Qin, T.-Y. Soo / Journal of Molecular Structure: THEOCHEM 897 (2009) 3235

on the system largely cancel out. Consequently, the two isomers

2.4 120
are very close in energy with C2v slightly favored. It is important
C1-C2

Bond distance (angstroms)

to point out that our calculated four orbitals (H-3 ? H in Fig. 1) 2.2 C1-O3

Bond angle (degrees)

O3-O4
are ordered differently in energy from those in Ref. [8], for which 110
O3-C1-O4
no conclusion can be drawn at this moment. 2.0
100
1.8
3.2. Transition state between D3h and C2v
1.6 90
A transition state was located on the ground state PES of CO3
(shown in Scheme 1). Its structural parameters and vibrational fre- 1.4 80
quencies are listed in Tables 1 and 2. IRC calculations were carried
out in both directions from TS to D3h and to C2v and the connection 1.2
70
between D3h and C2v on PES through the transition state was con-
1.0
rmed (shown in Fig. 3). The energy barrier from C2v to D3h is cal-
-2.0 -1.5 -1.0 -.5 0.0 .5 1.0 1.5 2.0
culated to be 5.0 kcal mol1 and 12.9 kcal mol1 from PW91PW91
Reaction coordinate ( amu1/2 bohr )
and B3LYP, respectively. The calculated PW91PW91 value is only
0.6 kcal mol1 larger than that of MRCI/6-311+G(3df) [7], while Fig. 2. Geometry change along the intrinsic reaction coordinate.
B3LYP did not provide a reasonable estimation. Reversely, the en-
ergy barrier from D3h to C2v is only 2.5 kcal mol1, implying a very
at potential energy surface around the D3h minimum, which Correspondingly, the O3C1O4 angle changes from 73 to 93
makes it very difcult to be tracked by experiments. On the other and from 0.71 Debye to 0.56 Debye for the molecular dipole. The
hand, the energy barrier for the interconversion between C2v iso- only imaginary frequency calculated for the transition state is
mers through the D3h intermediate is estimated to be only 421i cm1 and corresponds to a O3C1O4 bending mode. It is also
5.0 kcal mol1 (shown in Scheme 2), which means a very exible noticeable that two E0 stretching modes (1508 cm1) in D3h are
C2v structure. split into a B2 CO stretch of 1254 cm1 and another A1 C@O
Geometry change from D3h to C2v along the reaction coordinate stretch of 1631 cm1 in TS and nally turned into two stretching
is displayed in Fig. 2. From C2v to TS, C1O2 is lengthened by 0.036 modes of 917 cm1 and 2002 cm1 in C2v. However, in general all
to 1.215 , while C1O3 and C1O4 are shortened by 0.051 to bond distances and angles varies almost linearly along the reaction
1.291 . Larger bond distance change was observed for O3O4, coordinate and their values at TS are approximately the averages of
from 1.597 to 1.876 , showing that the bond is being cleaved. those in D3h and C2v.

3.3. Excited states of CO3

Table 2
Harmonic vibrational frequencies (cm1) and infrared intensities (km/mol) of CO3.
Excited states of CO3 were examined using TDDFT at the B3LYP/
Method B3LYP/aug-cc-pVQZ PW91PW91/aug-cc-pVQZ aug-cc-pVQZ and PW91PW91/aug-cc-pVQZ levels. However, the
Mode Symmetry Frequency Intensity Frequency Intensity two methods generated very similar results and only PW91PW91
results are listed in Table 3. For C2v, LUMO+1 is signicantly higher
C2v Isomer
Bend B2 567 5.6 539 4.0 in energy than LUMO (Fig. 1) and low-lying excited states are dom-
OPLA B1 669 31.5 645 23.3 inated by single excitations from highest occupied orbitals to
Bend B1 708 12.9 670 12.2 LUMO. It is noticeable that HOMO is only 0.17 eV higher in energy
CO stretch B2 923 67.5 917 71.8
than HOMO-1 and the lowest excited singlet state (11A1) is domi-
CO stretch A1 1123 12.7 1081 11.0
C@O stretch A1 2064 582.8 2002 507.7
nated by H-1 ? L, but not H ? L. For the latter (11B1), the transi-
tion energy is calculated to be 3.22 eV, 0.13 eV higher than that
D3h Isomer
Bend E0 288 3.7 325 0.6
OPLA A200 770 29.7 738 20.9
Stretch A10 1143 0.0 1093 0.0 Table 3
Stretch E0 1519 7.9 1508 19.9 Lowest eight excited singlet States of CO3 calculated by PW91PW91/aug-cc-pVQZ.a
C2v Transition state State Conguration C E (eV) E (nm) f
Bend A1 332i 27.5 421i 28.8
Bend B2 447 0.6 480 5.0 C2v Isomer
OPLA B1 754 30.4 701 22.4 1 1A1 H-1 ? L 0.69 3.09 402 0.0000
CO stretch A1 1142 0.7 1096 3.6 1 1B1 H?L 0.66 3.22 386 0.0004
CO stretch B2 1385 13.0 1254 36.4 1 1A2 H-2 ? L 0.70 4.28 289 0.0000
C@O stretch A1 1608 11.0 1631 27.7 1 1B2 H-3 ? L 0.58 6.75 184 0.0019
2 1A2 H-1 ? L+1 0.70 7.20 172 0.0000
OPLA, out-of-plane bending mode. 2 1B2 H ? L+1 0.57 7.28 170 0.0016
2 1A1 H-4 ? L 0.68 7.72 161 0.0000
3 1A2 H ? L+1 0.70 7.79 159 0.0000
D3h Isomer
1 1E00 H-1 ? L 0.62 1.13 1101 0.0000
O2 O2
2 1E00 H?L 0.62 1.13 1101 0.0000
O2
1 1 E0 H-2 ? L 0.49 3.05 407 0.0154
O4 C1 C1 2 1E00 H-3 ? L 0.49 3.05 407 0.0154
C1 1 1 A001 H-4 ? L 0.70 5.23 237 0.0000
O3 O4 3 1 E0 H-5 ? L 0.61 6.23 199 0.0463
O3 O4 O3 4 1 E0 H-6 ? L 0.61 6.23 199 0.0463
3 1E00 H ? L+2 0.70 8.94 139 0.0000
C2v D3h C2v
a
The dominant conguration (HOMO = H, LUMO = L), its coefcient (C), energy
Scheme 2. (eV, nm) and oscillator strength (f) are presented.
 C. Qin, T.-Y. Soo / Journal of Molecular Structure: THEOCHEM 897 (2009) 3235 35

are 11B1 and 11B2 with the latter more favored and they are con-
10.0 nected to 11E00 and 21E0 of D3h with signicant energy decrease.
5 1E'
The 11B2 state corresponds to HOMO-3 ? L and HOMO-3 and
9.0
1
3, 4 E" LUMO are mainly of r bonding and anti-bonding character on
O3O4, respectively. Once it is populated, the O3O4 bond should
3 1A2 be largely weakened and the D3h structure should be promoted. Fi-
1
8.0 2 B2 nally, CO3 will switch to D3h since it also lies signicantly lower in
3 1A2
2 1A1 energy. Next, if the system is quenched to its ground state, it will
1
7.0 2 1A2 2 B2 go back to C2v following the ground state potential energy curve.
1 B2
1 Therefore, it is very important to include enough electronic corre-
3, 4 1E' lation in determining the energy curve along C2vTSD3h since two
Relative energy ( eV )

6.0
isomers are favored by different electronic congurations at differ-
1 1A1" ent states.
5.0
4. Conclusions
1 1A2
4.0
We have studied CO3 using the DFT and TDDFT methods with
1
1 1 B1 different combinations of GGA functionals and correlation consis-
1, 2 E'
3.0 1 1A1 tent basis sets. The C2v isomer is calculated to be 2.5 kcal mol1
and 12.5 kcal mol1 lower in energy than D3h with a conversion en-
2.0 ergy barrier of 5.0 kcal mol1 and 12.9 kcal mol1 by PW91PW91
and B3LYP, respectively. All of the above include zero-point energy
1
1, 2 E" corrections. The geometry change along the reaction coordinate is
1.0
found to be almost linear and the TS structure is approximately an
average of D3h and C2v with an imaginary O3C1O4 bending mode
0.0
D3h S0 C2v S0 of 421i cm1. However, D3h is more favored in low energy excited
singlet states. These states also promote the C2v ? D3h conversion.

-1.0
-3.0 -2.0 -1.0 0.0 1.0 2.0 3.0 Acknowledgement
Reaction coordinate ( amu1/2bohr )
The support from Vassar College through its Undergraduate Re-
Fig. 3. Energy curves of the ground and excited singlet States of CO3. search Summer Institute (URSI) program is gratefully acknowl-
edged. The authors also want to thank the Computing and
of HOMO-1 ? LUMO, with a low oscillator strength of 0.0004, but Information Services (CIS) at Vassar College for providing comput-
the latter (H-1 ? L) is not allowed. The calculated transition energy ing time on their IBM Linux workstations.
is also very close to a value of 3.55 eV by EOM(2,3)/cc-pVTZ [8]
with the same electronic conguration. Two other excited singlet References
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