Quantum Mechanics: Methods

A single molecular formula can represent a number of molecular isomers. Each isomer is a
local minimum on the energy surface (called the potential energy surface, figura 1) created from
the total energy (i.e., the electronic energy, plus the repulsion energy between the nuclei) as a
function of the coordinates of all the nuclei. A stationary point is a geometric configuration such
that the derivative of the energy with respect to all displacements of the nuclei is zero.

Figura 1
A local (energy) minimum is a stationary point where all such displacements lead to an
increase in energy. The local minimum that is lowest is called the global minimum and
corresponds to the most stable isomer. If there is one particular coordinate change that leads
to a decrease in the total energy in both directions, the stationary point is a transition structure
and the coordinate is the reaction coordinate. This process of determining stationary points is
called geometry optimization.
The determination of molecular structure by geometry optimization became routine only
after efficient methods for calculating the first derivatives of the energy with respect to all
atomic coordinates became available. Evaluation of the related second derivatives allows the
prediction of vibrational frequencies if harmonic motion is estimated. More importantly, it
allows for the characterization of stationary points. The frequencies are related to the
eigenvalues of the Hessian matrix, which contains second derivatives. If the eigenvalues are all
positive, then the frequencies are all real and the stationary point is a local minimum. If one
eigenvalue is negative (i.e., an imaginary frequency), then the stationary point is a transition
structure. If more than one eigenvalue is negative, then the stationary point is a more complex
one, and is usually of little interest. When one of these is found, it is necessary to move the
search away from it if the experimenter is looking solely for local minima and transition
structures.
The total energy is determined by approximate solutions of the time-dependent Schrödinger
equation, usually with no relativistic terms included, and by making use of the Born-
Oppenheimer approximation, which allows for the separation of electronic and nuclear motions,
thereby simplifying the Schrödinger equation. This leads to the evaluation of the total energy as
a sum of the electronic energy at fixed nuclei positions and the repulsion energy of the nuclei.
Notable exceptions are certain approaches called direct quantum chemistry, which treat
electrons and nuclei on a common footing. Density functional methods and semi-empirical
methods are variants on the major theme. For very large systems, the relative total energies can
be compared using molecular mechanics. The ways of determining the total energy to predict
molecular structures are:
Ab initio methods
The programs used in computational chemistry are based on many different quantum-
chemical methods that solve the molecular Schrödinger equation associated with the molecular
Hamiltonian. Methods that do not include any empirical or semi-empirical parameters in their
equations - being derived directly from theoretical principles, with no inclusion of experimental
data - are called ab initio methods. This does not imply that the solution is an exact one; they
are all approximate quantum mechanical calculations. It means that a particular approximation
is rigorously defined on first principles (quantum theory) and then solved within an error margin
that is qualitatively known beforehand. If numerical iterative methods have to be employed, the
aim is to iterate until full machine accuracy is obtained (the best that is possible with a finite
word length on the computer, and within the mathematical and/or physical approximations
made).

The simplest type of ab initio electronic structure calculation is the Hartree-Fock (HF)
scheme, an extension of molecular orbital theory, in which the correlated electron-electron
repulsion is not specifically taken into account; only its average effect is included in the
calculation. As the basis set size is increased, the energy and wave function tend towards a limit
called the Hartree-Fock limit. Many types of calculations (known as post-Hartree-Fock methods)
begin with a Hartree-Fock calculation and subsequently correct for electron-electron repulsion,
referred to also as electronic correlation. As these methods are pushed to the limit, they
approach the exact solution of the non-relativistic Schrödinger equation. In order to obtain exact
agreement with experiment, it is necessary to include relativistic and spin orbit terms, both of
which are only really important for heavy atoms. In all of these approaches, in addition to the
choice of method, it is necessary to choose a basis set. This is a set of functions, usually centered
on the different atoms in the molecule, which are used to expand the molecular orbitals with
the LCAO (Linear Combination of Atomic Orbitals). Ab initio methods need to define a level of
theory (the method) and a basis set.

The Hartree-Fock wave function is a single configuration or determinant. In some cases,

particularly for bond breaking processes, this is quite inadequate, and several configurations
need to be used. Here, the coefficients of the configurations and the coefficients of the basis
functions are optimized together.

The total molecular energy can be evaluated as a function of the molecular geometry; in
other words, the potential energy surface. Such a surface can be used for reaction dynamics.
The stationary points of the surface lead to predictions of different isomers and the transition
structures for conversion between isomers, but these can be determined without a full
knowledge of the complete surface.

A particularly important objective, called computational thermochemistry, is to calculate

thermochemical quantities such as the enthalpy of formation to chemical accuracy. Chemical
accuracy is the accuracy required to make realistic chemical predictions and is generally
considered to be 1 kcal/mol or 4 kJ/mol. To reach that accuracy in an economic way it is
necessary to use a series of post-Hartree-Fock methods and combine the results. These methods
are called quantum chemistry composite methods.
Density Functional methods
Density functional theory (DFT) methods are often considered to be ab initio methods for
determining the molecular electronic structure, even though many of the most common
functionals use parameters derived from empirical data, or from more complex calculations.
This means that they could also be called semi-empirical methods. It is best to treat them as a
class on their own. In DFT, the total energy is expressed in terms of the total one-electron density
rather than the wave function. In this type of calculation, there is an approximate Hamiltonian
and an approximate expression for the total electron density. DFT methods can be very accurate
for little computational cost. The drawback is that, unlike ab initio methods, there is no
systematic way to improve the methods by improving the form of the functional. Some methods
combine the density functional exchange functional with the Hartree-Fock exchange term and
are known as hybrid functional methods.

Semi-empirical and empirical methods

Semi-empirical quantum chemistry methods are based on the Hartree-Fock formalism, but
make many approximations and obtain some parameters from empirical data. They are very
important in computational chemistry for treating large molecules where the full Hartree-Fock
method without the approximations is too expensive. The use of empirical parameters appears
to allow some inclusion of correlation effects into the methods.
Semi-empirical methods follow what are often called empirical methods, where the two-
electron part of the Hamiltonian is not explicitly included. For N-electron systems, this was the
Hückel method proposed by Erich Hückel , and for all valence electron systems, the Extended
Hückel method proposed by Roald Hoffmann.

Molecular mechanics
In many cases, large molecular systems can be modeled successfully while avoiding
quantum mechanical calculations entirely. Molecular mechanics simulations, for example, use a
single classical expression for the energy of a compound, for instance the harmonic oscillator.
All constants appearing in the equations must be obtained beforehand from experimental data
or ab initio calculations.
The database of compounds used for parameterization, i.e., the resulting set of parameters
and functions is called the force field, is crucial to the success of molecular mechanics
calculations. A force field parameterized against a specific class of molecules, for instance
proteins, would be expected to only have any relevance when describing other molecules of the
same class.
These methods can be applied to proteins and other large biological molecules, and allow
studies of the approach and interaction (docking) of potential drug molecules.

Methods for solids

Computational chemical methods can be applied to solid state physics problems. The
electronic structure of a crystal is in general described by a band structure, which defines the
energies of electron orbitals for each point in the Brillouin zone. Ab initio and semi-empirical
calculations yield orbital energies, therefore they can be applied to band structure calculations.
Since it is time-consuming to calculate the energy for a molecule, it is even more time-consuming
to calculate them for the entire list of points in the Brillouin zone.
Chemical dynamics
Once the electronic and nuclear variables are separated (within the Born-Oppenheimer
representation), in the time-dependent approach, the wave packet corresponding to the nuclear
degrees of freedom is propagated via the time evolution operator (physics) associated to the
time-dependent Schrödinger equation (for the full molecular Hamiltonian). In the
complementary energy-dependent approach, the time-independent Schrödinger equation is
solved using the scattering theory formalism. The potential representing the interatomic
interaction is given by the potential energy surfaces. In general, the potential energy surfaces
are coupled via the vibronic coupling terms.
The most popular methods for propagating the wave packet associated to the molecular
geometry are the split operator technique, the Multi-Configuration Time-Dependent Hartree
method (MCTDH), the semiclassical method.
Molecular dynamics (MD) examines (using Newton's laws of motion) the time-dependent
behavior of systems, including vibrations or Brownian motion, using a classical mechanical
description. MD combined with density functional theory leads to the Car-Parrinello method.

Interpreting molecular wave functions

The Atoms in Molecules model developed by Richard Bader was developed in order to
effectively link the quantum mechanical picture of a molecule, as an electronic wavefunction, to
chemically useful older models such as the theory of Lewis pairs and the valence bond model.
Bader has demonstrated that these empirically useful models are connected with the topology
of the quantum charge density. This method improves on the use of Mulliken population
analysis.

Fuente
http://en.wikipedia.org/wiki/Computational_chemistry

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