Computational chemistry
Computational chemistry is a branch of chemistry that uses computer simulation to
assist in solving chemical problems.[1] It uses methods of theoretical chemistry,
incorporated into computer programs, to calculate the structures and properties
of molecules, groups of molecules, and solids.[2] The importance of this subject stems
from the fact that, with the exception of some relatively recent findings related to the
hydrogen molecular ion (dihydrogen cation), achieving an accurate quantum
mechanical depiction of chemical systems analytically, or in a closed form, is not
feasible.[3] The complexity inherent in many-body problem exacerbates the challenge of
providing detailed descriptions in quantum mechanical systems.[4] While computational
results normally complement the information obtained by chemical experiments, it can
in some cases predict unobserved chemical phenomena.[5]
A dichromium metal complex with electrostatic field
surrounding it. Modelled using WebMO. [6]
Overview[edit]
Computational chemistry is different from theoretical chemistry. The term theoretical
chemistry may be defined as a mathematical description of chemistry,
whereas computational chemistry is usually used when a mathematical method is
sufficiently well developed that it can be automated for implementation on a computer.
In theoretical chemistry, chemists, physicists, and mathematicians
develop algorithms and computer programs to predict atomic and molecular properties
and reaction paths for chemical reactions.Computational chemists, in contrast, may
simply apply existing computer programs and methodologies to specific chemical
questions.[7]
Historically, computational chemistry has had two different aspects:
Computational studies, used to find a starting point for a laboratory synthesis or to
assist in understanding experimental data, such as the position and source of
spectroscopic peaks.[8]
Computational studies, used to predict the possibility of so far entirely unknown
molecules or to explore reaction mechanisms not readily studied via experiments.[8]
These aspects, along with computational chemistry's purpose, have resulted in a whole
host of algorithms.
History[edit]
Building on the founding discoveries and theories in the history of quantum mechanics,
the first theoretical calculations in chemistry were those of Walter Heitler and Fritz
London in 1927, using valence bond theory. The books that were influential in the early
development of computational quantum chemistry include Linus Pauling and E. Bright
Wilson's 1935 Introduction to Quantum Mechanics – with Applications to Chemistry,
[9]
Eyring, Walter and Kimball's 1944 Quantum Chemistry,[10] Heitler's 1945 Elementary
Wave Mechanics – with Applications to Quantum Chemistry,[11] and later Coulson's 1952
textbook Valence, each of which served as primary references for chemists in the
decades to follow.[12]
With the development of efficient computer technology in the 1940s, the solutions of
elaborate wave equations for complex atomic systems began to be a realizable
objective. In the early 1950s, the first semi-empirical atomic orbital calculations were
performed. Theoretical chemists became extensive users of the early digital computers.
One major advance came with the 1951 paper in Reviews of Modern Physics by
Clemens C. J. Roothaan in 1951, largely on the "LCAO MO" approach (Linear
Combination of Atomic Orbitals Molecular Orbitals), for many years the second-most
cited paper in that journal. A very detailed account of such use in the United Kingdom is
given by Smith and Sutcliffe.[13] The first ab initio Hartree–Fock method calculations on
diatomic molecules were performed in 1956 at MIT, using a basis set of Slater orbitals.
For diatomic molecules, a systematic study using a minimum basis set and the first
calculation with a larger basis set were published by Ransil and Nesbet respectively in
1960.[14] The first polyatomic calculations using Gaussian orbitals were performed in the
late 1950s. The first configuration interaction calculations were performed in Cambridge
on the EDSAC computer in the 1950s using Gaussian orbitals by Boys and coworkers.
[15]
By 1971, when a bibliography of ab initio calculations was published,[16] the largest
molecules included were naphthalene and azulene.[17][18] Abstracts of many earlier
developments in ab initio theory have been published by Schaefer.[19]
In 1964, Hückel method calculations (using a simple linear combination of atomic
orbitals (LCAO) method to determine electron energies of molecular orbitals of π
electrons in conjugated hydrocarbon systems) of molecules, ranging in complexity
from butadiene and benzene to ovalene, were generated on computers at Berkeley and
Oxford.[20] These empirical methods were replaced in the 1960s by semi-empirical
methods such as CNDO.[21]
In the early 1970s, efficient ab initio computer programs such as ATMOL, Gaussian,
IBMOL, and POLYAYTOM, began to be used to speed ab initio calculations of
molecular orbitals. Of these four programs, only Gaussian, now vastly expanded, is still
in use, but many other programs are now in use. At the same time, the methods
of molecular mechanics, such as MM2 force field, were developed, primarily by Norman
Allinger.[22]
One of the first mentions of the term computational chemistry can be found in the 1970
book Computers and Their Role in the Physical Sciences by Sidney Fernbach and
Abraham Haskell Taub, where they state "It seems, therefore, that 'computational
chemistry' can finally be more and more of a reality."[23] During the 1970s, widely different
methods began to be seen as part of a new emerging discipline of computational
chemistry.[24] The Journal of Computational Chemistry was first published in 1980.
Computational chemistry has featured in several Nobel Prize awards, most notably in
1998 and 2013. Walter Kohn, "for his development of the density-functional theory",
and John Pople, "for his development of computational methods in quantum chemistry",
received the 1998 Nobel Prize in Chemistry.[25] Martin Karplus, Michael Levitt and Arieh
Warshel received the 2013 Nobel Prize in Chemistry for "the development of multiscale
models for complex chemical systems".
