Constructing diabatic states from adiabatic states: Extending generalized Mulliken-Hush to multiple charge centers with Boys localization

Joseph E. Subotnik, Sina Yeganeh, Robert J. Cave, Mark A. Ratner

Research output: Contribution to journalArticlepeer-review

151 Scopus citations

Abstract

This article shows that, although Boys localization is usually applied to single-electron orbitals, the Boys method itself can be applied to many electron molecular states. For the two-state charge-transfer problem, we show analytically that Boys localization yields the same charge-localized diabatic states as those found by generalized Mulliken-Hush theory. We suggest that for future work in electron transfer, where systems have more than two charge centers, one may benefit by using a variant of Boys localization to construct diabatic potential energy surfaces and extract electronic coupling matrix elements. We discuss two chemical examples of Boys localization and propose a generalization of the Boys algorithm for creating diabatic states with localized spin density that should be useful for Dexter triplet-triplet energy transfer.

Original languageEnglish (US)
Article number244101
JournalJournal of Chemical Physics
Volume129
Issue number24
DOIs
StatePublished - Dec 1 2008

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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