Nonintuitive Diabatic Potential Energy Surfaces for Thioanisole

Shaohong L. Li, Xuefei Xu, Chad E. Hoyer, Donald G Truhlar

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


Diabatization of potential energy surfaces is a technique that enables convenient molecular dynamics simulations of electronically nonadiabatic processes, but diabatization itself is nonunique and can be inconvenient; the best methods to achieve diabatization are still under study. Here, we present the diabatization of two electronic states of thioanisole in the S-CH3 bond stretching and C-C-S-C torsion two-dimensional nuclear coordinate space containing a conical intersection. We use two systematic methods: the (orbital-dependent) 4-fold way and the (orbital-free) Boys localization diabatization method. These very different methods yield strikingly similar diabatic potential energy surfaces that cross at geometries where the adiabatic surfaces are well separated and do not exhibit avoided crossings, and the contours of the diabatic gap and diabatic coupling are similar for the two methods. The validity of the diabatization is supported by comparing the nonadiabatic couplings calculated from the diabatic matrix elements to those calculated by direct differentiation of the adiabatic states. (Graph Presented).

Original languageEnglish (US)
Pages (from-to)3352-3359
Number of pages8
JournalJournal of Physical Chemistry Letters
Issue number17
StatePublished - Sep 3 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.


  • conical intersection
  • diabatization
  • photochemistry
  • potential energy surfaces
  • thioanisole


Dive into the research topics of 'Nonintuitive Diabatic Potential Energy Surfaces for Thioanisole'. Together they form a unique fingerprint.

Cite this