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Constructing Diabatic States From Adiabatic States: Extending Generalized Mulliken–Hush To Multiple Charge Centers With Boys Localization, Joseph E. Subotnik, Robert J. Cave, Sina Yeganeh, Mark A. Ratner
Constructing Diabatic States From Adiabatic States: Extending Generalized Mulliken–Hush To Multiple Charge Centers With Boys Localization, Joseph E. Subotnik, Robert J. Cave, Sina Yeganeh, Mark A. Ratner
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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 …
An Ab Initio Study Of The Mono- And Difluorides Of Krypton, Gerald J. Hoffman, Laura A. Swafford '97, Robert J. Cave
An Ab Initio Study Of The Mono- And Difluorides Of Krypton, Gerald J. Hoffman, Laura A. Swafford '97, Robert J. Cave
All HMC Faculty Publications and Research
Results from ab initio calculations at the CCSD(T) level of theory are presented for krypton monofluoride (KrF), krypton monofluoride cation (KrF+), linear, ground-state krypton difluoride (KrF2), the triplet state of krypton difluoride, and the krypton–fluorine van der Waals complex (Kr–F2). These are the first calculations demonstrating that KrF is a bound molecule, in agreement with experimental observation. When corrected for basis-set superposition error, the calculated potential displays quantitative agreement with the attractive wall of the experimentally measured potential curve. Results are also presented for KrF+ and linear KrF2 which yield accurate values for their dissociation energies. The triplet state of …