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

220 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 - 2008

Funding

We thank Ryan Steele and Anthony Dutoi for very helpful discussions and Mike Schmidt for help with the GAMESS program. J.E.S. was supported by a NSF International Research Fellowship. S.Y. was supported by a NDSEG fellowship. R.J.C. was pleased to acknowledge support from the Harvey Mudd College. M.A.R. thanks the chemistry division of NSF and ONR, and the DOD MURI program for support.

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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