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CarParrinello molecular dynamics
The motion of small, but not too small, particles such as atoms and
molecules is usually well described by Lagrangian mechanics, with the
Lagrangian defined
as the kinetic energy minus the potential energy,

(21) 
leading to the set of Newtonian equations of motion for each particle ,
with mass and cartesian coordinate
:

(22) 
Numerical integration of the equations of motion, taking small time steps
, results in a trajectory through the hyperspace of all possible
positions and momenta of the particles, called phasespace. This simulation
technique is known as molecular dynamics (MD).
The motion of even smaller particles, such as electrons, cannot be
approximated with classical Newtonian dynamics, but instead has to
be described with the more accurate quantum mechanical equations of motion
derived from the timeindependent Schrödinger equation:

(23) 
That is, the Hamiltonian
, given as the sum of the
kinetic and potential energy operators, operating on the manyelectron
wave function gives us the energy . This rather simple and
very famous equation can unfortunately not be solved analytically
for a system of more than two electrons, and approximations on the
Hamiltonian have to be introduced. Following Kohn and Sham's
density functional theory (DFT) approach (see next section for
the details on DFT), the exact density and the exact energy can be obtained from
oneelectron wave functions, the KohnSham (KS) orbitals ,
which are solutions in a local potential. The heart of this machinery
lies in the notion that all properties, including the energy,
of the electronic system are a functional of the electron density, ,

(24) 
The KohnSham orbitals
can be expanded in an orthogonal basis
:

(25) 
with the expansion coefficients. The electron density ,
given as

(26) 
with the occupation number of KS orbital , gives us the probability
to find an electron at position .
In DFT, the sets of coefficients span a hyperspace , in which
a point representing orthonormal KS orbitals
thus corresponds to an energy , similar to a point in atomic coordinate
space corresponding to a potential energy . In fact, the iterative search
for the one point in that minimizes the energy to the physical groundstate
energy , resembles a molecular geometry optimization to minimize the
potential energy. Since we want the oneelectron functions to
be orthonormal, the trajectory through during the energy minimization
is constrained on a hypersurface in for which

(27) 
Taking the iteration steps as the analog of time steps, we can even formulate
Newtonian equations of motion for the ``dynamics'' of changing coefficients:

(28) 
Here, the are inertia parameters, usually called ``fictitious masses'',
which control the acceleration of the coefficients,
due to the force on the coefficients,
on the righthandside. The last term arises from the constraint
in equation 2.26, with the undetermined
Lagrange multipliers. The forces on the coefficients are given as

(29) 
which can amount to a considerable saving of computer time and memory with respect
to techniques based on diagonalization of the full Hamiltonian matrix.
In practice, the wave function coefficients are not known
a priori, and we start from a random set of , consistent with
equation 2.26, associated with a
meaningless energy via equations 2.23 and 2.24.
When we start to integrate the equations of motion (eq. 2.27),
the coefficients will accelerate towards configurations with lower energies
and gain ``kinetic energy'', until a dynamic equilibrium is reached. The
electronic groundstate energy is found by damping the coefficient
dynamics, so that kinetic energy is gradually removed and the coefficients
eventually freeze in the groundstate configuration. This technique to optimize
the wave function is known as ``simulated annealing''.
CarParrinello molecular dynamics (CPMD) is the integration of the fictitious wave
function coefficient dynamics with the classical molecular dynamics by a
single extended Lagrangian.
Starting from some atomic configuration in the
(optimized) electronic groundstate, we can calculate the forces on the
atoms using the HellmannFeynman theorem,

(31) 
to start the ab initio molecular dynamics. Initially,
the forces on the coefficients equal zero as the electronic configuration is
at its minimum, but after one time step the atomic positions have changed and
the wave function is no longer up to date. However, since the electronic
degrees of freedom and the atomic positions
are coupled
via the potential energy (equation 2.29), the forces on the
coefficients are no longer zero and the coefficients accelerate towards the
new electronic groundstate. When the fictitious coefficient masses
are chosen sufficiently small (i.e.
)
the response of the coefficients to the changing nuclei is so
rapid that the electrons remain to a sufficiently high degree in the
groundstate.
Figure 2.2:
Vibrational spectrum of the normal modes of the electronic
coefficients (solid line) for a system with a large gap (periodic super cell
containing 8 Si atoms in the diamond structure). The solid triangle indicates
the position of the highest ionic frequency. The vertical bars below the spectrum
represent the frequencies obtained from equation 2.31.
Figure from ref PaSmBu91.

Of course, the dynamics of the nuclei in CPMD has only physical meaning if
the electronic structure is close to its instantaneous groundstate at each
step of the simulation. In other words, the dynamics of the electronic coefficients
has to remain relatively cold. However, since the two dynamic subsystems
of nuclei
and electronic coefficients are coupled, in principle
energy can flow from the relatively hot nuclei subsystem, to the colder
coefficients, which would lead to deviations from the BornOppenheimer (groundstate)
surface. In many practical simulations, the energy flow between the subsystems can
be suppressed with a good choice for the fictitious coefficient masses ,
which can be rationalized by regarding the electronic coefficient dynamics
for small deviations from the groundstate, described as a superposition of
harmonic oscillations whose frequency is given by:
Here, indicates the eigenvalue of the th unoccupied and
the th occupied level, and the fictitious coefficient
masses are chosen equal for all .
As an illustration, let us refer to figure 2.2 from
the illuminating study of ref PaSmBu91, which shows the vibrational density
of states of the electronic coefficients for an unrealistic but instructive
model of crystalline silicon. The fictitious mass in this work was au.
The solid line is obtained from the Fourier transform of the velocity
autocorrelation function

(33) 
from a simulation of 3000 time steps ( au) and the vertical bars below
are obtained from equation 2.31. The lowest electronic
frequency (at about 1010 THz) results from the energy gap, which is in this model
eV, in good agreement with the estimate using
equation 2.31:
THz.
The highest ionic frequency for this model is 140 THz, indicated by the triangle
in figure 2.2. This clear separation between the characteristic
electronic and ionic frequencies, is the reason that the irreversible energy
transfer from the slow to the fast degrees of freedom is minimal, and the main
reason that CPMD works! Problems occur for systems with a small or vanishing
bandgap, such as semiconductors and metals, because the heat transfer can no longer
be controlled by choosing a small enough . A workable solution for these
systems can be provided by coupling both dynamical subsystems to thermostats
which remove kinetic energy from the electronic coefficients while adding kinetic
energy to the nuclei[19].
As the electronic coefficients rapidly fluctuate
around their optimal values, the instantaneous values of the forces do not
coincide with the HellmannFeynmann forces, however their average values do to
a very high degree of accuracy. The high efficiency of the CarParrinello
approach with respect to the socalled (real) BornOppenheimer molecular dynamics
(BOMD) method also lies in this respect. In BOMD, the electronic structure is
selfconsistently optimized after each time step in which only the relatively
small number of nuclei positions are propagated. In practice, the convergence
of the optimization has to be very high to avoid the accumulation of the small, but
systematic (!), deviations in the HellmannFeynman forces, which makes BOMD
computational more demanding than CPMD. This difference in efficiency is
partly reduced by the larger time step that can be used in BOMD, as the
maximum time step is limited by the proper integration of the equation of motions
of the fastest (i.e. lightest) particles, which are the high frequency
components of the fictitious dynamics in CPMD, whereas in BOMD, the lightest nuclei
limit the time step maximum.
A technique to accelerate CPMD further is known as
masspreconditioning[20], which is based on reducing these high
frequency components of the fictitious dynamics by properly scaling the
fictitious masses , so that a larger time step can be used.
Excellent reviews of the CarParrinello molecular dynamics techniques are
found in refs MaHuReview,ReMaReview,GaPaReview.
Figure 2.3:
Partial waves and projectors for Mn. Left panel:
partial waves (solid lines) and pseudo partial waves (dashed
and dashdotted lines). The ``first'' pseudo partial wave is a dashdotted line.
Right panel: first (solid line) and second (dashed line) projector functions. (a)
and (d) show the results for the first and second partial wave of the angular
momentum channel, respectively, (b) and (e) for the channel and (c) and (f)
for the channel. 3 and 3 functions are treated as valence states.
Figure from ref PAW.

The first CPMD implementations used a basis set of plane waves, in combination
with a pseudopotential[25,26,27], to expand the
oneelectron valence wave functions,
which is the most widely used approach in electronic structure calculations in
the field of solid state physics. Plane waves are of the form
( and the wave vector), which are
the eigenfunctions of Schrödinger's equation (2.22) for
an electron in vacuum with kinetic energy
. For
electrons in an external field, such as in atoms, however, an expansion in
plane waves is a rather poor choice, because these functions hardly mimic
the rapid fluctuations of the oneelectron wave functions in the neighborhood
of the nucleus. Usually the low lying core electrons are kept "frozen" during
an electronic structure calculation to reduce the computational cost, which is
a good approximation since these states remain practically invariant from
their atomic groundstate during the chemistry of bond breaking and making.
For the chemically active valence wave functions a pseudopotential is used
to describe the inner region (nucleus plus core electrons) of the atom, in a way that
allows for replacing the rapid fluctuating functions by more smooth functions.
Beyond this inner region, the smooth functions agree with the true wave functions.
A disadvantage of the pseudopotential method is that they become "very hard"
for first row elements and for systems with and electrons, so that
very large basis sets are required. An improvement on the traditional
pseudopotentials was provided with the development of Vanderbilt's ultrasoft
pseudopotentials [28,29] by relaxing on the norm conserving
condition that is usually imposed.
The simulations described in this thesis were performed with Blöchl's
CPMD implementation, named projector augmented wave or PAW[24],
which is based on a generalization of both the pseudopotential approach and the
linear augmentedplane wave method[30,31,32] (LAPW).
In contrast to the pseudopotential approach, the LAPW technique utilizes
the full oneelectron valence wave function with the correct nodal structure.
The wave function is subdivided into two regions; an inner (augmentation) region,
which is expanded in a basis set of localized functions, and an outer region
which is described by plane waves. At a certain (muffintin) sphere radius
from the nucleus, the partial wave functions are matched together by value
and derivative of the functions.
Instead in PAW, a linear transformation between the oneelectron valence wave functions
and fictitious pseudo wave functions is used, in Dirac's
bra and ket notation:

(34) 
where are a complete set of partial waves ( referring to the
atomic site , the angular momentum quantum numbers and the index
for different partial waves per and ). Each partial wave is
connected to a pseudo partial wave
, which only differs from
inside an augmentation region , and a localized, socalled,
projector function for which,

(35) 
As an illustration, we use figure 2.3 from ref PAW,
which shows the partial waves and projector functions for manganese.
The partial waves are functions on a radial grid, multiplied with spherical
harmonics, which are obtained by radially integrating Schrödinger's equation
for the isolated atom. The pseudo wave functions are expanded
in plane waves. In practice, the partial waves and
and
the projector functions are imported from an atomic calculation at
the start of a PAW molecular dynamics calculation.
The main advantages of the PAW approach compared to the conventional normconserving
pseudopotential methods is that the atomic partial and projector functions are better
transferable than pseudopotentials and that the full wave function is accessible, which
allows for the calculation of core dependent quantities such as
hyperfine parameters and electric field gradients[33,34].
Also a smaller plane wave basis set is required than with the norm conserving
pseudopotential methods, which is most important for the present study as it
cuts heavily on the computational expense.
A very detailed description of the PAW technique and its relation to the traditional
norm conserving pseudopotential method and the LAPW method is found
in reference PAW.
Next: Density Functional Theory
Up: Techniques
Previous: Reaction rate theory
Contents
Bernd Ensing
20030613