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12878 J. Phys. Chem.

1996, 100, 12878-12887

Ab Initio Molecular Dynamics Simulations

Mark E. Tuckerman, P. Jeffrey Ungar, Tycho von Rosenvinge, and Michael L. Klein*
Department of Chemistry, UniVersity of PennsylVania, Philadelphia, PennsylVania 19104-6323
ReceiVed: February 16, 1996X

Over the past decade, new simulation methodologies, such as the Car-Parrinello ab initio molecular dynamics
technique, have become increasingly important as tools to study and characterize condensed phase molecular
systems. We emphasize the versatility of these new approaches to simulation by reviewing selected applications
to molecular crystals, liquids, and clusters, which highlight a range of interesting phenomena. The molecular
crystals white phosphorus, nitromethane, and hydrogen chloride dihydrate exhibit molecular reorientation
phenomena, methyl torsional motion, and proton-hopping events, respectively. We indicate how, in the latter
examples, it is now possible to include quantum effects in the simulation of the proton motion. Ionic solvation
and proton transport in water are used to illustrate the current status of simulations of liquid systems. The
final topic in our survey deals with the possibility of including the quantum nature of nuclear motions into
the simulation methodology of clusters.

I. Introduction accessible from the neutron experiments, direct comparisons

with the simulation results7 on β-P4 are possible.
Classical molecular dynamics (MD), which has its origins in
As an example of a crystal system with a torsional degree of
the 1950s and 1960s, is now widely used to investigate
freedom, we consider the nitromethane crystal. Nitromethane
condensed phase systems, ranging from micellar solutions to
molecules contain a methyl group weakly bonded to an NO2
biomolecules, polymers, and inorganic materials. The standard
group. In the gas phase, the barrier against internal methyl
MD technique, which is based on the use of empirical
rotation about this bond is very small (∼6 cal/mol), which raises
interatomic potential functions parametrized to experimental
interesting questions concerning the nature of this motion in
data, has also proved its worth in the study of ionic solutions,
electrochemistry, tribology, and cluster science. One of the most the crystalline state. Since intermolecular interactions determine
exciting developments of the past decade is the advent of ab the dynamics of the crystal, there is the intriguing possibility
initio molecular dynamics, which, rather than requiring an of exploring the coupling between the rotational modes of each
empirical interaction potential as input, utilizes interatomic molecule and cooperative phenomena.
forces computed directly from the electronic structure. This Another aspect of molecular crystals that can be explored
new approach has now become established as an important tool using the CP scheme is the displacement of protons through
in the investigation of chemically complex environments. In hydrogen bonds.8 The study of such processes allows the
the Car-Parrinello (CP) approach1,2 to ab initio MD, the investigation of the role of structural relaxation involving other
electronic structure is described using the Kohn-Sham formula- nuclei and the assessment of the contribution of tunneling. As
tion3 of the density functional theory,4 and the Kohn-Sham an example, we consider the hydrogen chloride dihydrate
orbitals are expanded in a plane wave basis. The expansion crystal.9 Because of its low mass, the proton often exhibits
coefficients are treated as a set of fictitious dynamical variables quantum mechanical behavior, and so the usual approximation
that are propagated adiabatically with respect to the nuclei, so of classical nuclear motion is often too crude when applied to
that, at each time step, they describe the instantaneous ground proton transfer processes in molecular crystals. In order to
state Born-Oppenheimer surface. In this way, the need to solve incorporate quantum effects into the CP scheme, we must go
the Kohn-Sham equations explicitly is avoided. The CP beyond this approximation. As yet, there is no satisfactory
approach has proved useful in a wide variety of physical and method for obtaining true quantum dynamics at finite temper-
chemical applications. The present article illustrates the ver- ature, but it is possible to obtain quantum mechanical averages
satility of the CP approach to MD simulations by considering of equilibrium properties using the path integral approach.10-14
a variety of condensed phase systems. In the path integral formulation, the quantum canonical
The first examples presented concern the simulation of partition function, Tr(e-βH), is expressed as a sum over paths
molecular crystals. We begin with the low-symmetry, β-P4 in imaginary time that are periodic with a period equal to β )
phase crystal of white phosphorus. The common R-phase 1/kBT. In practice, the path integral is represented as a
transforms to the β-phase below 196 K, at atmospheric pressure. multidimensional integral over discretized paths, a form that is
The structure of this phase of phosphorus been determined5 equivalent to a closed, classical polymer chain with nearest-
using X-ray diffraction and verified6 using neutron scattering. neighbor harmonic coupling.15 Such an integral can be evalu-
The unit cell is triclinic and contains six somewhat distorted ated using MD techniques and therefore can be incorporated
tetrahedral P4 molecules with inversion symmetry only (space into the CP scheme. However, because of the stiffness of the
group P1h). The CPMD scheme allows the study of both the harmonic coupling, a straightforward MD approach will suffer
structure of this low-order phase and the reorientational dynam- from the fact that the trajectories will not be ergodic and hence
ics of the molecules, which are subject to weak intermolecular not sample the entire configuration space.16 However, a MD
forces. Since several aspects of the crystal dynamics are algorithm for path integrals exists11 that is almost as efficient
as more traditional Monte Carlo schemes. The algorithm
X Abstract published in AdVance ACS Abstracts, July 1, 1996. involves a change of variables that diagonalizes the harmonic
S0022-3654(96)00480-7 CCC: $12.00 © 1996 American Chemical Society
Molecular Dynamics Simulations J. Phys. Chem., Vol. 100, No. 31, 1996 12879

interaction and a coupling of each degree of freedom to a Nosé- in subsequent sections. A review of recent work on solvation
Hoover chain thermostat17 to ensure ergodic motion of the new and charge transport is then given, and future applications are
variables. discussed.
An important application of the CPMD simulation technique
presented here concerns the liquid state, the solvation of ions, II. Simulation Methodologies
and the transport of protons in ionic solutions. This work is A. Ab Initio Molecular Dynamics. The equations of motion
particularly compelling because it gives insight into the mech- for CPMD are derived from an extended Lagrangian in which
anism behind the anomalously high mobility of protons in electronic orbitals {φi} execute fictitious dynamics that allows
solution. In order to gain physical insight into this process, it them to follow the motion of nuclei having positions {RI} while
is essential to have access to the microscopic motion of remaining very close to the instantaneous ground state Born-
individual atoms during proton transfer events. Such informa- Oppenheimer surface. This is accomplished by keeping the
tion is often not obtainable experimentally but is given directly fictitious kinetic energy of the orbitals small compared to that
in a simulation. Since empirical potentials, which describe the of the nuclei and assigning to them a small fictitious mass
interaction of an hydronium ion with a solvent like water, are parameter µ. The interatomic forces are computed via the
difficult to construct, the ab initio approach is an attractive Hellman-Feynman theorem from the instantaneous electronic
alternative. Here, we will review and discuss recent work on structure at each nuclear configuration.
the solvation of H+ and OH- in liquid water.18 The ability not The extended Lagrangian takes the form
only to obtain solvation structures of these ions but also to shed
light on the physical mechanism and rate-limiting steps of proton L ) µ∑〈φ̇i|φ̇i〉 + 1/2∑MIR4 I2 - E[{φi},{RI}] +
transport in these systems is among the significant results of i I
this work.
In the above-mentioned applications of CPMD, quantum

Λij(〈φi|Ŝ({RI})|φj〉 - δij) (1)
effects of the proton are minimized by using deuterium instead
of hydrogen. In order to assess the importance of quantum where {MI} are the masses of the nuclei, and E[{φi},{RI}] is
effects on solvation and proton transport, a fully quantum the Kohn-Sham energy density functional given by
mechanical study of H+ and OH- in water should be carried
out. However, since these calculations are computationally 1 1 n(r) n(r′)
intensive, researchers have begun by considering small charged E[{φi},{RI}] ) - ∑ 〈φi|∇2|φi〉 + ∫dr dr′ +
water clusters, where long runs and good statistics can be
2 i 2 |r - r′|
collected with a more reasonable expenditure of CPU of time.19 Exc[n] + ∫dr Vloc(r) n(r) + ∑〈φi|V̂NL|φi〉 + U({RI}) (2)
Finally, we mention possible future applications of ab initio i
MD techniques in biological systems. At present, ab initio MD
methodology has been applied to small biological molecules20 In eq 2, the external potential is expressed in terms of an atomic
and has been used in an ambitious attempt to elucidate the pseudopotential that contains a local component Vloc(r) and a
mechanism of proton transport in an ion channel containing a nonlocal operator V̂NL. The use of pseudopotentials elimi-
strand of hydrogen-bonded water molecules.21 The results of nates22,24 the need to treat core electrons explicitly. The term
these studies are sufficiently encouraging to give optimism that “ion” is used to refer to the unit consisting of the nucleus with
as better algorithms are developed and enhanced computing core electrons attached. n(r) is the electronic density, Exc[n] is
power becomes available, even more complex biological the exchange and correlation functional, and U({RI}) is the ion-
systems can be investigated with the CPMD approach. ion interaction energy.
The last term in eq 1 is not technically part of the Lagrangian,
Although we do not provide a detailed discussion in this
but we have placed it here for convenience of notation. A
article, researchers have also applied MD to systems involving
problem arises because Lagrange’s equations of motion assume
other complications. For example, Silvestrelli et al.86 have
that independent variations can be made in the orbitals {φi},
studied molten Kx(KCl)1-x using a molecular dynamics tech-
but they are actually subject to a set of constraints
nique based on finite temperature DFT in order to incorporate
hot electrons. The CPMD method has also been extended to 〈φi|Ŝ({RI})|φj〉 ) δij (3)
allow the simulation of systems at constant pressure. Recent
applications discussed in the literature include the formation of These are incorporated in the last term of eq 1 using the method
hydrogenated amorphous carbon from the compression of of Lagrange multipliers.25 The multipliers Λij are chosen to
polyacetylene87 and the prediction of a new high-pressure phase ensure the fulfillment of the constraints while allowing the
of ice.58 Finally, it is occasionally possible to obtain MD equations of motion to be obtained from Hamilton’s variational
trajectories on an excited state potential energy surface, such principle. Note that eq 3 takes the form of a generalized
as in the work of Bernasconi et al.88 on the solid state orthonormality condition.22 The Hermitian overlap operator Ŝ
polymerization of acetylene under pressure. In this case, a triplet is given by Ŝ({RI}) ) Î + P̂({RI}). The imposition of this
exciton self-trapped on a single, cis-bent molecule is incorpo- constraint condition allows the use of ultrasoft pseudopotentials
rated using the local spin density approximation. with eq 1, which also require augmentation of the electronic
The paper is organized as follows: In section IIA, the CP charge density n(r).22 For norm-conserving pseudopotentials,
Lagrangian and equations of motion are reviewed. The discus- P̂ is zero and Ŝ reduces to an identity operator, which gives the
sion is generalized to allow the use of ultrasoft pseudopoten- usual orthonormality constraint. For ultrasoft pseudopotentials,
tials22 for treatment of core electrons and involves the use of P̂ is composed of projectors onto functions that characterize
the recently introduced constraint nonorthogonal orbital (CNO) the pseudopotential. Details of the implementation of ultrasoft
method.23 In section IIB, the path integral CP method is pseudopotentials in CPMD are given in the literature.26
discussed, and the MD algorithm11 is described and compared Because the constraints couple both electronic and ionic
to more straightforward approaches. Applications of these degrees of freedom (through the dependence of Ŝ on RI), the
methods to the molecular crystals mentioned above are presented usual SHAKE and RATTLE27,28 procedures used to enforce
12880 J. Phys. Chem., Vol. 100, No. 31, 1996 Tuckerman et al.

them must be iterated through the ionic positions. This can be seen by writing down the imaginary time path integral
complication can be avoided by introducing a transformation expression for the quantum canonical partition function in the
of the electronic orbitals from the set {φi} to a new set {ψi} Born-Oppenheimer limit.32 With the approximation that the
given by |φi〉 ) ∑j|ψj〉Tji. The transformation matrix T ) O-1/2, temperature kBT ) 1/β is small compared to the gap in the
where Oij ) 〈ψi|Ŝ({RI})|ψj〉 is the matrix element of the operator electronic spectrum, the path integral expression for the partition
Ŝ with respect to the new orbitals.23,29,30 Both O and therefore function takes the form
T are Hermitian. Thus, given the definition of the orbital
transformation, the constraints in eq 3 are satisfied by construc- N
Z ) ∫D[R1]...D[RN] exp{- ∫0 dτ [∑1/2MIR4 I2(τ) +
tion. The orbitals {ψi} are used instead of {φi} to rewrite the
CP Lagrangian. Since eq 3 is satisfied implicitly, no explicit I)1

constraint on the new orbitals is required. However, for use in E0({RI(τ)})]} (7)
a MD scheme, an arbitrary set of constaint conditions, σR[{ψi}]
) 0, is imposed on the orbitals {ψi} in order to prevent them where E0({RI}) is the ground state energy surface (see ref 13
from becoming linearly dependent. Incorporating the new for details). Equation 7 can be written as the limit of a
orbitals and ad hoc constraints into the CP Lagrangian gives discretized “classical phase space” integral:10

L ) µ∑〈ψ̇i|ψ̇i〉 + 1/2∑MIR4 I2 - ∑Mji〈ψi|Ĥ|ψj〉 + N

i I i,j Z ) lim [∏N ∫dRI(1)...dRI(P)∫dPI(1)...dPI(P)] ×

∑R ΛRσR[{ψi}]
{ [∑ ( )
Pf∞ I)1
P N (PI(s))2
exp - β∑ + MIωP2(RI(s) - RI(s+1))2 +
where Ĥ is the Kohn-Sham Hamiltonian and M ) O-1.An 2M′I 2

s)1 I)1
alternative formulation of the energy density functional in terms
of nonorthogonal orbitals has been presented by Mauri and 1
E0({RI}(s)) (8)
Galli.31 While no explicit matrix inversion is required in their P
scheme, departures from the exact energy density functional
can occur when the orbitals are not at the precise minimum, where {RI}(s) denotes the set of all nuclear positions at imaginary
making their approach less suitable for MD. time slice s, ωP is the chain frequency xP/β, {M′I} is a set of
The equations of motion derived from eq 4 are fictitious bead masses, and N is an overall normalization
constant. The path periodicity condition RI(P+1) ) RI(1) is
µ|ψ̈i〉 ) |φ̃i〉 + ∑ΛR
assumed. Note that the Gaussian integral over the fictitious
∂〈ψi| momenta simply yields a temperature-dependent prefactor. From
eq 8, it can be seen that the ground state energy surface must
2 I ) FI + Tr(HδI)
MIR (5) be evaluated at each imaginary time slice, a fact requiring the
introduction of a set of Kohn-Sham orbitals for each time
where (∆I)ij ) 〈φi|∇IŜ|φj〉. FI is the force that would be derived slice.12
from eq 1, and Hij is the matrix element of the Kohn-Sham Equation 8 can be evaluated for finite (but large) P using
Hamiltonian with respect to the orthogonal orbitals Hij ) molecular dynamics techniques. An extended Lagrangian
〈φi|Ĥ|φj〉. The transformed electronic force |φ̃i〉 is given by corresponding to eq 8 can be constructed12-14 that leads to the
following set of equations of motion:
|φ̃i〉 ) - ∑(Ĥ|φj〉 - ∑Ŝ|φk〉〈φk|Ĥ|φj〉)Tji (6)
j k ∂σR
µ|ψ̈i(s)〉 ) |φ̃i(s)〉 + ∑Λ(s)
This is just the usual electronic force rotated by the matrix Tji R ∂〈ψi(s)|
and with Λij replaced by 〈φi|Ĥ|φj〉.
While the constrained nonorthogonal orbital (CNO) method (s)
1 ∂Ẽ
requires that some condition be imposed, a simpler condition 2 I(s) ) -MIωP2(2RI(s) - RI(s+1) - RI(s-1)) -
MIR (9)
than eq 3 can be chosen. In particular, the simple orthonormality P ∂R(s)
constraint, 〈ψi|ψj〉 ) δij, and the norm constraint, 〈ψi|ψi〉 ) 1,
conditions have been investigated and shown to be satisfactory where Ẽ is the energy density functional expressed in terms of
choices.23 For norm constraints, it is necessary to monitor the the nonorthogonal orbitals: Ẽ(s) ) ∑i,j Mji(s)〈ψ(s)
i |Ĥ |ψj 〉.
(s) (s)
off-diagonal elements of the overlap matrix 〈ψi|ψj〉. If they are Equation 9 can, in principle, generate the quantum canonical
observed to grow beyond a specified tolerance, the orbitals must distribution. However, due to the presence of stiff harmonic
be rotated using the unitary transformation that diagonalizes this forces arising from the quantum kinetic energy, the sampling
matrix. This operation will set the off-diagonal elements once efficiency will be very poor.16 An efficient PIMD algorithm
again to zero but will not effect the dynamics, since the CP exists11 that employs a change of variables to the staging modes
Lagrangian is invariant under unitary transformation in the space used in path integral Monte Carlo calculations.33-36 The use
of occupied states. A tolerance of 10-3 has been found to be of staging coordinates has the effect of diagonalizing the
sufficiently small to maintain a stable scheme.23 The norm quantum kinetic energy. In addition, each degree of freedom
constraint has the advantage that it constitutes only N conditions is coupled to a Nosé-Hoover chain thermostat17 to ensure that
as opposed to the N2 conditions required by the full orthonor- the motion of each mode is ergodic. This method has recently
mality constraint. been incorporated into the CP scheme.14 The staging transfor-
B. Ab Initio Path Integral Molecular Dynamics. Quantum mation is defined by
corrections to the equilibrium properties of the ionic subsystem
can be computed by applying the CP method to path integral *
uI(1) ) RI(1), uI(s) ) RI(s) - RI(s) (s ) 2, ..., P) (10)
(PI) molecular dynamics.12-14 The validity of this approach
Molecular Dynamics Simulations J. Phys. Chem., Vol. 100, No. 31, 1996 12881
where RI(s) ) [(s - 1)RI(s+1) + RI(1)]/s. The inverse staging
transformation can be expressed as a recursion:

s - 1 (s+1) 1 (1)
RI(1) ) uI(1), RI(s) ) uI(s) + RI + RI
s s
(s ) 2, ..., P) (11)

The s ) P term is used to start the recursion using the path

periodicity condition RI(P+1) ) RI(1). A more general form of
the staging transformation that is useful for very large P is given
in ref 11.
The staging transformation is substituted into eq 8 as a change Figure 1. Cumulative average of the primitive energy estimator (au)
of variables, giving the following expression for the partition in eq 16 for a path integral simulation of a single H2O molecule using
function: various approaches: eqs 9 (method I), ref 13 (method II), and the
methods discussed in the text (method III).
Z ) lim [∏N ′ ∫duI(1)...duI(P) ∫dPI(1)...dPI(P)] ×
the electronic subsystem. The thermostat forces are given by

{ [( )
Pf∞ I)1 1
GI,l,1 ) M′I(s)(ŭI,l ) -
(s) 2
P N (PI(s))21 β
exp -β∑ ∑ + MI(s)ωP2 (uI(s))2 +
2M′(s) 2 1 1
[ ] [ ]
s)1 I)1
GI,l,M-1 ) QR(ξ̇I,l,M-2
)2 - + QR(ξ̇I,l,M
(s) 2
) -
β β
E0({RI(uI(1),...,uI(P))}(s)) (12) 1
GI,l,ν ) QR(ξ̇I,l,ν-1
)2 - ν ) 2, ..., Mion - 2, Mion

1 ) ν∑〈ψ̇i |ψ̇i 〉 - Ee
where the masses MI(s) replace the physical masses MI and are γ(s) (s) (s)
referred to as the “staging masses”. They are given by MI(1) ) i
MI and MI(s) ) sMI/(s - 1) for s ) 2, ..., P. The fictitious
masses M′I(s) are assumed to be a constant multiple of the
staging masses, i.e., M′I(s) ) cMI(s). The notation {RI
) QM-2(η̆M-2
)2 -
βe ] [
+ QM(η̆M ) -
(s) 2 1
βe ]
(uI(1),...,uI(P))}(s) is intended to indicate that, at each time slice s,
the elements of the set {RI}(s) of Cartesian bead positions for γκ(s) ) Qκ-1(η̆κ-1 ) -
(s) 2
κ ) 2, ..., Melec - 2, Melec (14)
the different atoms are functions of all the staging variables βe
uI(1),...,uI(P). In order to produce the distribution in eq 12, the Using the recursive inverse transformation, eq 11, the forces
following set of equations of motion is employed: on the staging modes can be computed straightforwardly in
∂σR terms of the primitive forces - ∂Ẽ(s)/∂RI,l

µ|ψ̈i(s)〉 ) |φ̃i(s)〉 + ∑Λ(s)

R 1 |ψ̇i 〉
- µη̆(s) (s)
1 ∂Ẽ P ∂Ẽ(s)
R ∂〈ψi |
(s) 1
P ∂u(1)
) ∑
I,l I,l
1 ∂Ẽ

[ ]
) -MI(s)ωP2 uI,l
- - M′I(s)ξ̇I,l,1
(s) (s)
P ∂u(s) (s) (s)
I,l 1 ∂Ẽ 1 (s - 2) ∂Ẽ
) + (15)
P ∂u(s) P (s - 1) ∂u(s-1) ∂R(s)
I,l I,l I,l
QRξ̈I,l,ν ) GI,l,ν
- QRξ̇I,l,ν
(s) (s)
ξ̇I,l,ν+1 ν ) 1, ..., Mion - 1
Although eqs 13 and 15 have been written for the staging
modes, they could have equally well been written in terms of
QRξ̈I,l,M ) (s)
GI,l,M - (s)
QRξ̇I,l,M-1 (s)
the normal modes of the chain.37 A comparison between staging
and normal modes was carried out in ref 14, and the two
Qκη̈κ(s) ) γκ(s) - Qκη̆κ(s)η̆κ+1
κ ) 1, ..., Melec - 1 approaches were found to exhibit equal sampling efficiency.
These methods were also compared to the primitive scheme
QMη̈M ) γM
- QMη̆M-1
(s) (s)
η̆M (13) given in eqs 9 and to the method proposed in ref 13. The results
of this comparison are shown in Figure 1, where the convergence
In eqs 13, the index l ) x, y, z runs over the Cartesian of the primitive energy estimator
components of vectors uI(s). Both the electronic and the ionic P N
3NP 1
- ∑ ∑ MIωP2 (RI(s) - RI(s+1))2 +
subsystems have been coupled to independent sets of chain
Eprim )
thermostats of lengths Melec and Mion, respectively. For the ions, 2β s)1 I)1 2
each Cartesian component of each mode variable is coupled to
1 P
its own Nosé-Hoover chain thermostat with the thermostat mass
parameter QR ) 1/(βωP2). For the electrons, a single thermostat ∑
E[{ψi}(s),{RI}(s)] (16)
chain is used with masses Q1 ) 2Ee/ωe2 and Qκ ) 2Ee/(Neωe2),
where Ee is the desired electron kinetic energy, ωe is a for the four methods is plotted. The system studied consisted
characteristic frequency of the fictitious electron dynamics, and of a single water molecule in a box of length 5.3 Å with periodic
Ne is the number of fictitious dynamical degrees of freedom in boundary conditions at a temperature of 100 K with P ) 32.
12882 J. Phys. Chem., Vol. 100, No. 31, 1996 Tuckerman et al.

Further details of this comparison can be found in ref 14. In

Figure 1 the cumulative average of the estimator in eq 16 over
a runs of length 10 000 steps is shown. It can be seen from the
figure that the method described above with either staging or
normal modes converged significantly faster than the other two
approaches. Since PICP calculations are extremely demanding
computationally due to the requirement of P sets of Kohn-
Sham orbitals, the increased sampling efficiency afforded by
the method described above can result in a substantial savings
in CPU time.
III. White Phosphorus at Low Temperatures
Both the R (room temperature) and β (low temperature)
phases of white phosphorus consist of tetrahedral P4 molecules,
Figure 2. Pair distribution functions for phosphorus atoms taken from
but until the past 10 years there has been little structural data
simulations of white phosphorus at 50 and 145 K (offset for clarity).
on either phase. The room temperature form is thought to be The inset, which shows the intramolecular peak near 2.2 Å in enhanced
body-centered cubic (lattice parameter a ) 18.51 ( 0.03 Å) detail, reveals the distortion of the phosphorus tetrahedral.
with 56 or more molecules per cell (space group I4h3m-Td3).38
The low-temperature phase is now known to have a triclinic
unit cell (at 50 K, a ) 11.45 Å, b ) 5.503 Å, c ) 11.26 Å, R
) 71.84°, β ) 90.37°, and γ ) 71.56°) containing six P4
molecules.5,6 The neutron scattering experiments tend to
confirm earlier speculation39 that R-P4 is a rotator phase while
β-P4 is an orientationally ordered crystal.
We performed ab initio CPMD simulations of β-P4 at 50 and
145 K using the coordinates obtained from the reduction of the
neutron data as a starting point. A system consisting of two
unit cells along the b axis was used to even out the overall
simulation cell dimensions and to avoid unduly constraining
the phonon modes along this direction. The standard ap-
proach40,41 was used for the local density approximation (LDA)
to the exchange-correlation functional. Since the LDA has been
found to fail badly in the case of weak interactions,42,43 we have
added gradient corrections (GC) to the functional, which have
been shown to give a much better description of weakly bonded
systems.43,44 They are taken from Becke45 for the exchange
and Perdew46 for the correlation. The phosphorus core electrons
Figure 3. Power spectral densities of the molecular center-of-mass
were treated using a generalized norm-conserving pseudopo- velocities (a) and (b) angular velocities taken from simulations of white
tential.24,47 The electronic orbitals were expanded in plane phosphorus at 50 and 145 K.
waves using a cutoff of 12 Ry. The plane wave coefficients
were given a mass µ ) 850 au, and the time step was set to δt The modes due to molecular translation and rotation may be
) 7 au. Constant volume trajectories spanning about 10 ps separately analyzed using the power spectral densities of the
were generated for the two temperatures. molecular center-of-mass translational and angular velocities.
Before proceeding with the MD calculations, the crystal (The angular velocity of a vibrating molecule can be calculated
structure was allowed to relax fully. This resulted in very little from its instantaneous angular momentum and inertia tensor
change except that the (∼3%) distortions from ideal tetrahedral about its center of mass.) Figure 3 shows the resulting spectra
molecules, which were found experimentally, mostly disap- for (a) translation and (b) rotation. Both span a range from
peared. Subsequent analysis of the MD trajectories showed that low frequency to 100 cm-1, which implies a correlation time
these distortions reappeared at finite temperature, suggesting for the velocities of ∼0.33 ps. There is little difference between
that they are a dynamical effect and not an artifact of the
the angular velocity spectra for the two temperatures. If a
reduction of the neutron scattering data. Figure 2 shows the
transition to a rotator phase had occurred, we would expect a
time-averaged pair distribution function for the phosphorus
significant increase in the spectral density at low frequencies.
atoms. The inset shows satellite peaks near the base of the main
The rotational motion is therefore mostly libration with a center
peak, which corresponds to the typical P-P bond length of 2.23
frequency in the vicinity of 40 cm-1, which is in fair agreement
Å. The main peak contains a little more than two of the three
nearest neighbors. Therefore, the remaining atom is found, on with inelastic neutron scattering measurements below the β f
average, at a distance about -2% to +4% different from the R transition temperature.6 These show peaks centered near 27
other two. cm-1 at 50 K and 20 cm-1 at 180 K, extending to 80-100
The frequencies present in the system are obtained by cm-1.
calculating the power spectral density of the atomic velocities, Casual inspection of snapshots of the system at times 4-8
which may be obtained either from the autocorrelation functions ps apart shows that the molecules do succeed in rotating
〈v(t)·v(0)〉 or equivalently from summing the spectral densities completely around, but it is not clear whether or not the
of all the velocity components. The resulting spectrum shows molecules are orientationally disordered. Further insight into
sharp peaks at 337, 434, and 575 cm-1 from the internal the reorientational dynamics may be gained through the use of
molecular vibrations. These are red-shifted by about 30 cm-1 the tetrahedral rotor functions Mn(Ω), n ) 1-7, which are
from published frequencies for the isolated P4 molecule.48 suitable normalized combinations of the seven l ) 3 spherical
Molecular Dynamics Simulations J. Phys. Chem., Vol. 100, No. 31, 1996 12883

Figure 4. Mean reorientational correlation functions from CPMD Figure 5. Atomic velocity power spectrum for solid nitromethane at
simulation of white phosphorus at 50 and 145 K. The curves shown T ) 285 K.
are averages over the normalized autocorrelation functions of the seven
tetrahedral rotor functions; i.e., R(t) ) ∑n)1
Rn(t). enough that rotational reorientation could be observed. Fur-
thermore, in earlier neutron scattering experiments with an
harmonics. In Cartesian coordinates, they are
energy resolution of 0.053 meV, no definite resolution of the
M1 ) (27/16)1/2∑xyz (17) tunnel splitting of rotational states was possible,51 suggesting
that tunneling phenomena have a negligible effect on the
M2 ) (9/320)1/2∑(5x2 - 3xr2)
rotational motion at temperatures near the melting point. Hence,
(18) the approximation of classical nuclei is sufficient to study the
dynamics of the nitromethane crystal, and the techniques
M5 ) (27/64)1/2∑x(y2 - z2) (19) described in section IIA can be applied.
Ab initio MD simulations were performed using two unit cells
where r ) (x,y,z) is a unit vector from the center of a molecule (eight molecules) of the crystal (orthorhombic, space group
to one of its atoms. The rotor functions not listed, n ) 3, 4 P21212152). The lattice parameters were taken to be a ) 5.404
and n ) 6, 7, are obtained by cyclic permutation of the (x,y,z) Å, b ) 6.513 Å, and c ) 8.996 Å, which allows for a small
variables in the M2 and M5 functions, respectively. The sum is thermal expansion from the T ) 0 values. Core electrons were
to be taken over all for atoms for a given molecule, and the treated using Vanderbilt’s ultrasoft pseudopotential scheme,22
normalization is fixed as ∑n)1
Mn2 ) 1.49 and a plane wave cutoff of 35 Ry was used. Exchange was
The rotor functions can serve as rotational order parameters treated using the gradient corrected functional of Becke,45 while
for the system. For example, if the phase is orientationally correlation was treated within the LDA. The electron mass
disordered but only Td-type orientations are present (with respect parameter µ ) 600 au, and the time step δt ) 5 au. The
to the selected x, y, and z axes), then 〈M1〉 ) 0 but 〈M12〉 ) 1. equations of motion were integrated using the reversible CP
Our simulations show that β-P4 has persistent orientational order method based on Gauss’ equations as described in ref 56. In
at both temperatures studied, since 〈Mn〉 * 0. It happens that addition, combining the scaled mass scheme56 with nonorthogo-
the expectation values for the n ) 6 rotor function are nal orbitals gives roughly a factor of 3 savings over standard
particularly large, which indicates that one D2d orientation is approaches to CP dynamics with Vanderbilt pseudopotentials.84
favored (corresponding to one bond aligned with the z axis and A trajectory of total length 4 ps was generated. The temperature
the opposite bond aligned with the x axis). More information was set at T ) 285 K, just below the melting point, to allow
that can quantify the reorientation dynamics is available from sufficient rotational reorientation to occur over the course of
the autocorrelation of the rotor functions the simulation.
In Figure 5 the frequency spectrum is shown, which is
Rn(t) ) 〈Mn(t) Mn(0)〉/〈Mn2〉 (20) computed from either the velocity component power spectral
densities or the Fourier transforms of the velocity autocorrelation
For illustration, Figure 4 shows averages over all seven functions. This shows the frequencies present in the system.
autocorrelation functions for both temperatures. The long-term In order to obtain intensities, it is necessary to compute the
memory of the phase is indicated by the nonzero final value of dipole moment spectra or autocorrelation functions.53 Since the
the autocorrelation at long times ≈〈Mn〉2/〈Mn2〉. (The horizontal pure modes measured by IR spectroscopy in the crystal (T )
lines represent the final values for the two temperatures 78 K)54 and liquid (T ) 354 K)55 are not substantially different,
estimated from the values of 〈Mn〉 and 〈Mn2〉.) On the other some comparison with the results presented here is possible.
hand, the rapid decay to the vicinity of the final value represents The spectrum shown in Figure 5 exhibits the same qualitative
the short-term memory loss. From the graph, the time scale features of the IR spectra.54,55 The use of ultrasoft pseudopo-
for this decay is in the 0.4 ps range, which is consistent with tentials often leads to a small red shift in the observed
the estimated angular velocity correlation time discussed earlier. frequencies. In Figure 5, there is a consistent 2%-6% red shift
in comparison to measured spectra.
IV. Dynamics of the Nitromethane Crystal
We can attempt to examine the contributions from the motions
The nitromethane crystal (CH3NO2) was studied as an of the methyl and nitrate groups separately by computing the
example of a system in which rotational motion of a methyl velocity power spectra of only the hydrogens and only the
group plays an important role. In the gas phase, the barrier oxygens, respectively. The resulting hydrogen vibration spec-
against rotation of the unit about the C-N axis is very small trum retains all the qualitative features of the full spectrum,
(about 6 cal/mol).50 This raises the possibility that in the solid which means that, at the temperature considered, the rotation
state (melting point 301.7 K) the barrier might remain small of the methyl group is coupled to the other modes of the
12884 J. Phys. Chem., Vol. 100, No. 31, 1996 Tuckerman et al.

molecule. Similarly, the oxygen vibration spectrum exhibits quantum simulation, which was started from this new config-
many of the features of the full spectrum, except for the high- uration, showed no signs of returning to the original structure.
frequency CH stretching modes. From these results it can be We minimized both of these configurations and found that
concluded that a one-dimensional model, based only on the while they were both stable the shifted one had an energy that
rotation angle θ, would likely be insufficient to describe properly was approximately 0.015 hartree lower. This energy difference
the rotational motion of the methyl group at this temperature. is fairly small and probably within the accuracy of our use of
DFT; furthermore, it is possible that while the correct structure
V. Crystalline Hydrogen Chloride Dihydrate has a lower energy in nature, the shifted structure may have an
energy only slightly higher. The imposition of a fixed simula-
Hydrogen chloride dihydrate is a monoclinic crystal with tion cell based on the experimental parameters may also force
space group P21/c. The lattice parameters are9 a ) 3.991 Å, b the model system to assume the new structure. It will be
) 12.055 Å, c ) 6.698 Å, and β ) 100.58°. The structure necessary to let the cell parameters vary to find the minimum-
contains puckered layers of Cl- ions connected by hydrogen energy configuration without this constraint. It may also be
bonds from water molecules. These water molecules are held necessary to construct a better pseudopotential for chlorine that
together in pairs by a short hydrogen bond (2.41 Å), forming takes into account more than just the outermost valence electron
H5O2+ ions. Such a crystal could present an interesting of the chlorine atom, based on experience gained in the
opportunity to study quantum contributions to the motion of simulation of other systems involving Cl. Although we have
the proton in the hydrogen bond joining the two water molecules found the BLYP functional to be the best available for this work,
in each H5O2+Cl- unit. Since the H5O2+ ions appear in an it may also be inadequate for a system as complex as this one.
ordered, crystalline environment, it is expected that quantum These results help to stress that great care must be taken when
effects may be important. Thus, the methods presented in modeling hydrogen-bonded systems.
section IIB were applied with the hope of comparing the
quantum and classical CP calculations. VI. Hydronium and Hydroxyl Ions in Liquid Water
The system simulated consisted of a single unit cell of the
crystal (containing four H5O2+Cl- units) at a temperature of Spectroscopic experiments in solution60-62 and diffraction
200 K. As in the previous example, Vanderbilt pseudopotentials studies of hydrated crystals63 were able to show that charge
were used to treat core electrons. A plane wave cutoff of 30 defects introduced by excess or missing protons in water occur
Ry and the Becke corrections to the exchange with Lee-Yang- naturally in the form of the hydronium (H3O+) and hydroxyl
Parr functional (BLYP)89 were used along with an electron mass (OH-) ions, referred to as the “water ions”. Recent ab initio
parameter of µ ) 600 au and a time step of 5 au. Path integral simulations have been able to verify these results.18,64 These
simulations were performed using 32 water molecules in a box
CP calculations were carried out using the staging MD approach
of length 9.8 Å with an added or missing proton. Vanderbilt
with P ) 8. While this value of P is probably too small for
ultrasoft pseudopotentials were used to treat the core electrons.
the chosen temperature, it is sufficiently large to make a
Becke’s gradient-corrected functional was used for the exchange,
qualitative comparison between the quantum and classical
and the correlation was treated within the LDA. The electronic
simulation results. The fictitious masses of the ions were chosen
orbitals were expanded in plane waves up to a cutoff of 25 Ry.
to be twice their physical values (i.e., M′I ) 2MI, M′I(s) ) When solvated, the H3O+ ion is observed to form hydrogen
2MI(s)). Nosé-Hoover chain thermostat lengths of Melec ) 4 bonds to three neighboring water molecules to make an H9O4+
and Mion ) 4 and mass parameters determined by 4ωP and ωp solvation complex. The existence of this complex had been
were coupled to the electrons and ions, respectively. The predicted by Eigen and De Maeyer in the late 1950s.65 These
thermostated equations of motion, eqs 13, were integrated using simulations have also predicted that the OH- ion forms a
the techniques described in ref 14 with a seventh-order Suzuki/ fourfold coordinated solvation complex in which the ligands
Yoshida integrator for the thermostats. The equations were lie in a single plane that is roughly perpendicular to the OH-
evolved for 24 000 and 8000 steps for the classical and quantum bond axis. These two “species” will be referred to as primary
systems, respectively. We checked the convergence of the solvation complexes. Proton migration is observed to occur
simulation by plotting the cumulative average of both the via the Grotthuss mechanism,66 which is characterized by a
primitive (cf. eq 16) and virial57 energy estimators. Both series of proton “hopping” events from one oxygen site to
estimators show convergence within the first 1000 steps for both another. These hopping events are actually successive transfers
the quantum and classical simulations. of protons through the hydrogen bonds along a contiguous path
Although we wished to study the properties of the proton in in the hydrogen bond network. During a Grotthuss event,
the O-O hydrogen bond, this goal has not yet been achieved. intermediate complexes are observed to occur. In the H+ case,
The simulation proceeded smoothly at first, but after ap- this complex is the H5O2+ complex in which the excess proton
proximately 1 ps in the classical simulation the configuration is located midway along the hydrogen bond joining two water
of the system changed. In the true crystalline structure, each molecules. This complex has received considerable attention
H5O2+ molecule hydrogen bonds to four chlorine atoms. In in the literature (for a review, see ref 67). In the OH- case,
the new shifted configuration, two of the H5O2+ molecules have the intermediate complex is a tetrahedral H7O4- complex.
rotated slightly in such a way that one of each of their hydrogen Figures 6 and 7 show the radial distribution functions gO*O and
atoms (which used to be bonded to a chlorine atom) has shifted gO*H, where O* denotes the oxygen atom in H3O+ or OH-.
and now bonds to the other oxygen atom. Thus, an infinite Figure 6 shows the radial distribution functions for each
chain of oxygen atoms hydrogen bonded together is formed. solvation complex (H9O4+ and H5O2+) in comparison to the
Since one of these oxygens is bonded to four hydrogens and distribution functions for pure water.44 Similarly, Figure 7
the other to three hydrogens, the structure is hydronium that is shows the radial distribution functions for the H9O5- and H7O4-
bonded twice to water (to a water molecule in the same unit complexes. In both cases the solvation shells are shorter than
cell and the equivalent one in the next cell along the a axis). the ordinary water-water H bond. However, in the OH- case,
Although the other two H5O2+ molecules maintain their form, these H bonds are somewhat longer, and hence weaker, than
their bonding pattern to the chlorine atoms is different. The those in the H3O+ solvation shell. Rough measurements of the
Molecular Dynamics Simulations J. Phys. Chem., Vol. 100, No. 31, 1996 12885

Figure 6. Oxygen-oxygen (top) and oxygen-hydrogen (bottom) Figure 7. Oxygen-oxygen (top) and oxygen-hydrogen (bottom)
radial distribution functions for H+ in water. The distribution functions radial distribution functions for OH- in water. The distribution
are measured with respect to the hydronium oxygen (O*). In each functions are measured with respect to the hydroxyl oxygen (O*). In
figure, the solid line and short dashed line respectively correspond to each figure, the solid line and short dashed line respectively correspond
the subset of configurations in which the H5O2+ and H9O4+ complexes to the subset of configurations in which the H7O4- and H9O5-
are present. The long dashed curves are the O-O and O-H radial complexes are present. The long dashed curves are the O-O and O-H
distribution functions for pure water, taken from the simulations of radial distribution functions for pure water, taken from the simulations
Laasonen et al.84 of Laasonen et al.84

lifetimes of these complexes in solution as well as studies of 105° angle between the OH- bond axis and the ligands and
them in vacuum suggest that they are stable and hence can be can easily accept the transferring proton, thus forming a water
referred to as secondary complexes. A Grotthuss hop is molecule. These geometrical differences are responsible for the
accompanied by a reorganization of the local hydrogen bond distinction in activity of the two complexes. There is, in
network to accommodate the formation of a solvation complex addition, a secondary rate-limiting step in the OH- case. In
on a new site. Thus, a solvation complex is observed to migrate the active state, the H7O4- complex is hydrogen-bonded to three
through the hydrogen bond network, giving rise to a structural neighboring water molecules, each of which is solvated by four
diffusion model of proton migration.68-71 neighbors. As in the H+ case, a fluctuation in the coordination
The H+ and OH- systems are qualitatively different. In the number of one of these molecules from 4 to 3 must precede
H+ case, the H9O4+ complex is “active” in the sense that it is proton transfer so that the active complex can be re-formed at
the diffusing structure, moving from site to site via formation the new site, and once again second solvation shell dynamics
of the H5O2+ intermediate. In the OH- case, the H9O5- plays a role in the proton transfer process. On the other hand,
complex is “inactive” owing to the presence of a distinct since the dominant rate-limiting step is the formation of the
solvation shell around it. The active H7O4- complex forms upon active complex from the inactive one (which also depends on
breaking of one of the hydrogen bonds in the plane defined by the breaking of a hydrogen bond), second solvation shell
the OH- bond axis. It is this active complex that is observed dynamics can only be said to have a secondary effect here.
to diffuse through the network.
VII. Charged Water Clusters
Further analysis of the simulated trajectories have allowed
the rate-limiting step in proton transfer for each system to be As a prelude to understanding the possible role of quantum
identified. In the case of H+, a change in the coordination effects in ion solvation charged water clusters, two prototypical
number of a water molecule in the first solvation shell of the species, H5O2+ and H3O2-, have been investigated.19 The
hydronium ion (i.e., second solvation shell dynamics) from 4 simulation studies employed the pseudopotential scheme of
to 3 allows the hydronium structure to migrate to the low- Martins and Troullier72 with a cutoff of 70 Ry and the so-called
coordinated site. In the case of OH-, the analysis reveals that BLYP functional to treat exchange and correlation.45,73 Each
purely geometrical factors determine which of the two solvation complex was placed at the center of a cubic box with length 8
complexes permits structural diffusion. In the H9O5- complex, Å to which cluster boundary conditions were applied.85 Nuclear
the angle between the ligands and the OH- bond axis is roughly quantum effects have been incorporated using the path integral
90°. Thus, proton transfer from water molecules in the first CP techniques described above.19 The same clusters have been
solvation shell to the OH- site is hindered since a new water studied by traditional quantum chemical techniques.74-76
molecule with an angle of 90° would form as a result of the Figures 8 and 9 show contours of the two-dimensional
transfer. By contrast, the H7O4- complex has an approximately distribution function of ROO (the oxygen-oxygen distance) and
12886 J. Phys. Chem., Vol. 100, No. 31, 1996 Tuckerman et al.

Figure 8. Contours of the two-dimensional distribution function of Figure 9. Contours of the two-dimensional distribution function of
the oxygen-oxygen distance, ROO, and the asymmetric stretch coor- the oxygen-oxygen distance, ROO, and the asymmetric stretch coor-
dinate, d12 ) rO1H* - rO2H*, for the isolated H5O2+ complex at 300 K. dinate, d12 ) rO1H* - rO2H*, for the isolated H3O2- complex at 300 K.
H* denotes the shared proton. The top curve shows the results from H* denotes the shared proton. The top curve shows the results from
a CP simulation using the classical nuclei approximation. The bottom a CP simulation using the classical nuclei approximation. The bottom
curve shows the results from a path integral CP simulation. curve shows the results from a path integral CP simulation.

the asymmetric stretch coordinate (d12 ) rO1H* - rO2H*, where enough that the proton has a high probability of being located
H* is the shared proton). These figures show the results for midway between the oxygens.
both the classical and path integral simulations of each complex.
In the path integral simulations, P ) 16 imaginary time VIII. Summary and Future Outlook
discretizations were used.
The results of the simulations suggest that, at a temperature This article has focused on a few applications of ab initio
of 300 K, quantum effects in the H5O2+ cluster do not MD simulations to condensed phase problems linked to physical
significantly alter the qualitative classical picture, in which the chemistry. Codes for classical equilibrium MD simulations of
proton is most likely to be found midway between the two such systems have been available commercially for some time.
oxygen atoms. Comparing quantum and classical simulations Their use is spreading and, while they are gaining in sophistica-
at the same temperature, one can see that the quantum tion, the field of nonequilibrium molecular dynamics (NEMD)83
distribution function describing the spatial location of the proton still presents unique challenges.78-82 The methodology of purely
is somewhat wider than the classical one but that the general classical equilibrium MD also continues to evolve.77 The topics
features of these distributions are the same. In the H3O2- we have discussed show that it is now possible to carry out
cluster, however, quantum effects appear to alter even the MD simulations of condensed phase systems without recourse
qualitative picture. The classical distribution has a definite to empirical parameters to describe the interatomic interactions.
bimodal character in which the proton is located on either one Even the quantum mechanical behavior of the nuclear motion
oxygen site or the other. However, in the quantum picture, the is now accessible via path integral CPMD methods. Although
proton is most likely to be located midway between the oxygen the system sizes that can be ordinarily handled at the present
atoms, as in the case of positive charge. time (typically, a few hundred atoms) are modest compared to
These results are consistent with the picture obtained from classical MD simulations with empirical potentials, ab initio
the ion solvation simulations. The hydrogen bonds in the first MD methods will no doubt grow in importance. For example,
solvation shell of the hydronium ion are short, and therefore in the future to investigate the function of an enzyme, it will
the potential surface felt by the proton is not likely to have a likely become a routine procedure to use empirical potentials
large barrier. In the hydroxyl simulations, however, the to handle the protein and its host environment, while using ab
hydrogen bonds in the solvation shell of both the active and initio techniques for the active site of interest. A future
inactive complexes are long (∼2.5-2.7 Å), probably leading challenge will be to develop more rigorous approaches and
to the presence of a significant barrier. The results of the cluster simulation methodologies for such mixed quantum-classical
calculations suggest that quantum effects soften this barrier schemes.
Molecular Dynamics Simulations J. Phys. Chem., Vol. 100, No. 31, 1996 12887

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