Quantum mechanical computations on very large molecular systems: The local self‐consistent field method

Vincent Théry, Daniel Rinaldi, Jean‐Louis ‐L Rivail, Bernard Maigret, G. Ferenczy

Research output: Contribution to journalArticle

275 Citations (Scopus)

Abstract

Quantum chemical computations on a subset of a large molecule can be performed, at the neglect of diatomic differential overlap (NDDO) level, without further approximation provided that the atomic orbitals of the frontier atoms are replaced by parametrized orthogonal hybrid orbitals. The electrostatic interaction with the rest of the molecule, treated classically by the usual molecular mechanical approximations, is included into the self‐consistent field (SCF) equations. The first and second derivatives of energy are obtained analytically, allowing the search for energy minima and transition states as well as the resolution of Newton equations in molecular dynamics simulations. The local self‐consistent field (LSCF) method based on these approximations is tested by studying the intramolecular proton transfer in a Gly‐Arg‐Glu‐Gly model tetrapeptide, which reveals an excellent agreement between a computation performed on the whole molecule and the results obtained by the present method, especially if the quantum subsystem includes the side chains and the peptidic unit in between. The merits of the LSCF method are examplified by a study of proton transfer in the Asp69—Arg71 salt bridge in dihydrofolate reductase. Simulations of large systems, involving local changes of electronic structure, are therefore possible at a good degree of approximation by introducing a quantum chemical part in molecular dynamics studies. This methodology is expected to be very useful for reactivity studies in biomolecules or at the surface of covalent solids. © 1994 by John Wiley & Sons, Inc.

Original languageEnglish
Pages (from-to)269-282
Number of pages14
JournalJournal of Computational Chemistry
Volume15
Issue number3
DOIs
Publication statusPublished - 1994

Fingerprint

Local Field
Proton transfer
Molecules
Molecular dynamics
Approximation
Degree of Approximation
Transition State
Tetrahydrofolate Dehydrogenase
Local System
Biomolecules
Electronic Structure
Reactivity
Second derivative
Coulomb interactions
Energy
Set theory
Molecular Dynamics
Salt
Electrostatics
Molecular Dynamics Simulation

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

Quantum mechanical computations on very large molecular systems : The local self‐consistent field method. / Théry, Vincent; Rinaldi, Daniel; Rivail, Jean‐Louis ‐L; Maigret, Bernard; Ferenczy, G.

In: Journal of Computational Chemistry, Vol. 15, No. 3, 1994, p. 269-282.

Research output: Contribution to journalArticle

Théry, Vincent ; Rinaldi, Daniel ; Rivail, Jean‐Louis ‐L ; Maigret, Bernard ; Ferenczy, G. / Quantum mechanical computations on very large molecular systems : The local self‐consistent field method. In: Journal of Computational Chemistry. 1994 ; Vol. 15, No. 3. pp. 269-282.
@article{0f9fe253b027425d980d73e1cdf61b54,
title = "Quantum mechanical computations on very large molecular systems: The local self‐consistent field method",
abstract = "Quantum chemical computations on a subset of a large molecule can be performed, at the neglect of diatomic differential overlap (NDDO) level, without further approximation provided that the atomic orbitals of the frontier atoms are replaced by parametrized orthogonal hybrid orbitals. The electrostatic interaction with the rest of the molecule, treated classically by the usual molecular mechanical approximations, is included into the self‐consistent field (SCF) equations. The first and second derivatives of energy are obtained analytically, allowing the search for energy minima and transition states as well as the resolution of Newton equations in molecular dynamics simulations. The local self‐consistent field (LSCF) method based on these approximations is tested by studying the intramolecular proton transfer in a Gly‐Arg‐Glu‐Gly model tetrapeptide, which reveals an excellent agreement between a computation performed on the whole molecule and the results obtained by the present method, especially if the quantum subsystem includes the side chains and the peptidic unit in between. The merits of the LSCF method are examplified by a study of proton transfer in the Asp69—Arg71 salt bridge in dihydrofolate reductase. Simulations of large systems, involving local changes of electronic structure, are therefore possible at a good degree of approximation by introducing a quantum chemical part in molecular dynamics studies. This methodology is expected to be very useful for reactivity studies in biomolecules or at the surface of covalent solids. {\circledC} 1994 by John Wiley & Sons, Inc.",
author = "Vincent Th{\'e}ry and Daniel Rinaldi and Rivail, {Jean‐Louis ‐L} and Bernard Maigret and G. Ferenczy",
year = "1994",
doi = "10.1002/jcc.540150303",
language = "English",
volume = "15",
pages = "269--282",
journal = "Journal of Computational Chemistry",
issn = "0192-8651",
publisher = "John Wiley and Sons Inc.",
number = "3",

}

TY - JOUR

T1 - Quantum mechanical computations on very large molecular systems

T2 - The local self‐consistent field method

AU - Théry, Vincent

AU - Rinaldi, Daniel

AU - Rivail, Jean‐Louis ‐L

AU - Maigret, Bernard

AU - Ferenczy, G.

PY - 1994

Y1 - 1994

N2 - Quantum chemical computations on a subset of a large molecule can be performed, at the neglect of diatomic differential overlap (NDDO) level, without further approximation provided that the atomic orbitals of the frontier atoms are replaced by parametrized orthogonal hybrid orbitals. The electrostatic interaction with the rest of the molecule, treated classically by the usual molecular mechanical approximations, is included into the self‐consistent field (SCF) equations. The first and second derivatives of energy are obtained analytically, allowing the search for energy minima and transition states as well as the resolution of Newton equations in molecular dynamics simulations. The local self‐consistent field (LSCF) method based on these approximations is tested by studying the intramolecular proton transfer in a Gly‐Arg‐Glu‐Gly model tetrapeptide, which reveals an excellent agreement between a computation performed on the whole molecule and the results obtained by the present method, especially if the quantum subsystem includes the side chains and the peptidic unit in between. The merits of the LSCF method are examplified by a study of proton transfer in the Asp69—Arg71 salt bridge in dihydrofolate reductase. Simulations of large systems, involving local changes of electronic structure, are therefore possible at a good degree of approximation by introducing a quantum chemical part in molecular dynamics studies. This methodology is expected to be very useful for reactivity studies in biomolecules or at the surface of covalent solids. © 1994 by John Wiley & Sons, Inc.

AB - Quantum chemical computations on a subset of a large molecule can be performed, at the neglect of diatomic differential overlap (NDDO) level, without further approximation provided that the atomic orbitals of the frontier atoms are replaced by parametrized orthogonal hybrid orbitals. The electrostatic interaction with the rest of the molecule, treated classically by the usual molecular mechanical approximations, is included into the self‐consistent field (SCF) equations. The first and second derivatives of energy are obtained analytically, allowing the search for energy minima and transition states as well as the resolution of Newton equations in molecular dynamics simulations. The local self‐consistent field (LSCF) method based on these approximations is tested by studying the intramolecular proton transfer in a Gly‐Arg‐Glu‐Gly model tetrapeptide, which reveals an excellent agreement between a computation performed on the whole molecule and the results obtained by the present method, especially if the quantum subsystem includes the side chains and the peptidic unit in between. The merits of the LSCF method are examplified by a study of proton transfer in the Asp69—Arg71 salt bridge in dihydrofolate reductase. Simulations of large systems, involving local changes of electronic structure, are therefore possible at a good degree of approximation by introducing a quantum chemical part in molecular dynamics studies. This methodology is expected to be very useful for reactivity studies in biomolecules or at the surface of covalent solids. © 1994 by John Wiley & Sons, Inc.

UR - http://www.scopus.com/inward/record.url?scp=84986492373&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84986492373&partnerID=8YFLogxK

U2 - 10.1002/jcc.540150303

DO - 10.1002/jcc.540150303

M3 - Article

AN - SCOPUS:84986492373

VL - 15

SP - 269

EP - 282

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 3

ER -