Finding Free-Energy Landmarks of Chemical Reactions

Motoyuki Shiga, Mark 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
DOIs
StateAccepted/In press - Jan 1 2018

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landmarks
Free energy
Chemical reactions
chemical reactions
ascent
free energy
Potential energy surfaces
descent
saddle points
Electronic structure
Demonstrations
potential energy
sampling
Sampling
electronic structure
aqueous solutions
Derivatives
temperature dependence
Water
rings

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this

Finding Free-Energy Landmarks of Chemical Reactions. / Shiga, Motoyuki; Tuckerman, Mark.

In: Journal of Physical Chemistry Letters, 01.01.2018, p. 6207-6214.

Research output: Contribution to journalArticle

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