Finding Free-Energy Landmarks of Chemical Reactions

Motoyuki Shiga, Mark E. Tuckerman

Research output: Contribution to journalArticle

Abstract

We propose a novel approach to search for free-energy landmarks, i.e., minima and the saddle points, of chemical reactions in an automated manner using a combination of steepest descent and gentlest ascent methods. A numerical approach is suggested to improve the sampling efficiency of the second derivatives of the free-energy surface, which is required in the gentlest ascent method. This technique opens a way to identify free-energy landmarks of bond-breaking/creating processes in which the underlying potential energy surface is described using on-the-fly electronic structure calculations. As demonstrations of the approach, we present applications to the ring-opening of cis-1,2-dimethylbenzocyclobutene using the semiempirical PM7 method, focusing on the temperature dependence of the paths and barrier of the reaction, and we study an SN2 reaction in aqueous solution using a semiempirical QM/MM approach combining PM7 with the TIP3P water model.

Original languageEnglish (US)
Pages (from-to)6207-6214
Number of pages8
JournalJournal of Physical Chemistry Letters
Volume9
Issue number21
DOIs
StatePublished - Nov 1 2018

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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