An adiabatic molecular dynamics method for the calculation of free energy profiles

Lula Rosso, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

A new molecular dynamics method for calculating free energy profiles for rare events is presented. The new method is based on the creation of an adiabatic separation between the reaction co-ordinate subspace and the remaining degrees of freedom within a molecular dynamics run. This is achieved by associating with the reaction coordinate(s) a high temperature and large mass, thereby allowing the activated process to occur while permitting the remaining degrees of freedom to respond adiabatically. In this limit, by applying a formal multiple time scale Liouville operator factorization, it can be rigorously shown that the free energy profiles are obtained directly from the probability distribution of the reaction coordinate subspace and, therefore, require no postprocessing of the output data. The new method is applied to a variety of model problems and its performance tested against free energy calculations using the "bluemoon ensemble" approach. The comparison shows that free energy profiles can be calculated with greater ease and efficiency using the new method.

Original languageEnglish (US)
Pages (from-to)91-112
Number of pages22
JournalMolecular Simulation
Volume28
Issue number1-2
DOIs
StatePublished - Jan 1 2002

Fingerprint

Molecular Dynamics
Free energy
Molecular dynamics
Free Energy
free energy
molecular dynamics
profiles
degrees of freedom
Degree of freedom
Subspace
Multiple Time Scales
Rare Events
Factorization
Post-processing
factorization
Probability distributions
Mathematical operators
Ensemble
Probability Distribution
operators

Keywords

  • AFED
  • Energy profiles
  • Harmonic oscillator
  • Isomerization
  • Molecular dynamics

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

An adiabatic molecular dynamics method for the calculation of free energy profiles. / Rosso, Lula; Tuckerman, Mark.

In: Molecular Simulation, Vol. 28, No. 1-2, 01.01.2002, p. 91-112.

Research output: Contribution to journalArticle

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