TY - JOUR
T1 - Derivation of Force Fields for Molecular Mechanics and Dynamics from ab initio Energy Surfaces
AU - Maple, Jon R.
AU - Dinur, Uri
AU - Hagler, Arnold T.
PY - 1988/8
Y1 - 1988/8
N2 - We present a technique for addressing the problem of deriving potential
energy functions for the simulation of organic, polymeric, and
biopolymeric systems, as well as for modeling vibrational spectroscopic
properties. This method is designed to address three major objectives:
deriving and comparing optimal functional forms for describing the
energies of molecular deformations and interactions, developing a
technique to rapidly and objectively determine reasonable force
constants for intermolecular and intramolecular interactions, and
determining the transferability of these potential forms and constants.
The first two of these objectives are addressed in this paper, while the
latter problem will be treated elsewhere. The technique uses ab initio
molecular energy surfaces, which are described by the energy and its
first and second derivatives with respect to coordinates. As an example,
application to a small model compound (i.e., the formate anion) is
given. A variety of analytical forms for the potential are tested
against the data, to find which forms are best. The importance of
anharmonicity and cross terms in accounting for structure and energy, as
well as for dynamics, is demonstrated and a more accurate representation
of the out-of-plane deformation for a trigonal center is derived from
the energy surfaces.
AB - We present a technique for addressing the problem of deriving potential
energy functions for the simulation of organic, polymeric, and
biopolymeric systems, as well as for modeling vibrational spectroscopic
properties. This method is designed to address three major objectives:
deriving and comparing optimal functional forms for describing the
energies of molecular deformations and interactions, developing a
technique to rapidly and objectively determine reasonable force
constants for intermolecular and intramolecular interactions, and
determining the transferability of these potential forms and constants.
The first two of these objectives are addressed in this paper, while the
latter problem will be treated elsewhere. The technique uses ab initio
molecular energy surfaces, which are described by the energy and its
first and second derivatives with respect to coordinates. As an example,
application to a small model compound (i.e., the formate anion) is
given. A variety of analytical forms for the potential are tested
against the data, to find which forms are best. The importance of
anharmonicity and cross terms in accounting for structure and energy, as
well as for dynamics, is demonstrated and a more accurate representation
of the out-of-plane deformation for a trigonal center is derived from
the energy surfaces.
U2 - 10.1073/pnas.85.15.5350
DO - 10.1073/pnas.85.15.5350
M3 - Article
C2 - 16593959
SN - 0027-8424
VL - 85
SP - 5350
EP - 5354
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 15
ER -