Finite-Temperature Dimer Method for Finding Saddle Points on Free Energy Surfaces

Huan Zhang, Lili Qiu, Dan Hu

Research output: Contribution to journalArticle

Abstract

The dimer method and its variants have been shown to be efficient in finding saddle points on potential surfaces. In the dimer method, the most unstable direction is approximately obtained by minimizing the total potential energy of the dimer. Then, the force in this direction is reversed to move the dimer toward saddle points. When the finite-temperature effect is important for a high-dimensional system, one usually needs to describe the dynamics in a low-dimensional space of reaction coordinates. In this case, transition states are collected as saddle points on the free energy surface. The traditional dimer method cannot be directly employed to find saddle points on a free energy surface since the surface is not known a priori. Here, we develop a finite-temperature dimer method for searching saddle points on the free energy surface. In this method, a constrained rotation dynamics of the dimer system is used to sample dimer directions and an efficient average method is used to obtain a good approximation of the most unstable direction. This approximated direction is then used in reversing the force component and evolving the dimer toward saddle points. Our numerical results suggest that the new method is efficient in finding saddle points on free energy surfaces.

Original languageEnglish (US)
JournalJournal of Computational Chemistry
DOIs
StatePublished - Jan 1 2019

Fingerprint

Dimer
Finite Temperature
Saddlepoint
Dimers
Free energy
Free Energy
Temperature
Unstable
Surface Potential
Transition State
Temperature Effect
Surface potential
Potential energy
Thermal effects
High-dimensional
Direction compound
Numerical Results
Approximation
Energy

Keywords

  • dimer method
  • free energy surface
  • rare event
  • saddle point
  • transition path

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

Finite-Temperature Dimer Method for Finding Saddle Points on Free Energy Surfaces. / Zhang, Huan; Qiu, Lili; Hu, Dan.

In: Journal of Computational Chemistry, 01.01.2019.

Research output: Contribution to journalArticle

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