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Full-Text Articles in Physics
The Initial And Final States Of Electron And Energy Transfer Processes: Diabatization As Motivated By System-Solvent Interactions, Joseph E. Subotnik, Robert J. Cave, Ryan P. Steele, Neil Shenvi
The Initial And Final States Of Electron And Energy Transfer Processes: Diabatization As Motivated By System-Solvent Interactions, Joseph E. Subotnik, Robert J. Cave, Ryan P. Steele, Neil Shenvi
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For a system which undergoes electron or energy transfer in a polar solvent, we define the diabatic states to be the initial and final states of the system, before and after the nonequilibrium transfer process. We consider two models for the system-solvent interactions: A solvent which is linearly polarized in space and a solvent which responds linearly to the system. From these models, we derive two new schemes for obtaining diabatic states from ab initio calculations of the isolated system in the absence of solvent. These algorithms resemble standard approaches for orbital localization, namely, the Boys and Edmiston–Ruedenberg (ER) formalisms. …
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 Specific Solvent Effects On The Electronic Coupling Element In Electron Transfer Reactions, Thomas M. Henderson '98, Robert J. Cave
An Ab Initio Study Of Specific Solvent Effects On The Electronic Coupling Element In Electron Transfer Reactions, Thomas M. Henderson '98, Robert J. Cave
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Specific solvent effects on the electronic coupling element for electron transfer are examined using two model donor–acceptor systems (Zn2+ and Li2+) and several model “solvent” species (He, Ne, H2O, and NH3). The effects are evaluated relative to the given donor–acceptor pair without solvent present. The electronic coupling element (Hab) is found to depend strongly on the identity of the intervening solvent, with He atoms decreasing Hab, whereas H2O and NH3 significantly increase Hab. The distance dependence (essentially exponential decay) is weakly affected by a single intervening solvent atom–molecule. However, when the donor–acceptor distance increases in concert with addition of successively …
A Semiclassical Model For Orientation Effects In Electron Transfer Reactions, Robert J. Cave, Stephen J. Klippenstein, R.A. Marcus
A Semiclassical Model For Orientation Effects In Electron Transfer Reactions, Robert J. Cave, Stephen J. Klippenstein, R.A. Marcus
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An approximate solution to the single‐particle Schrödinger equation with an oblate spheroidal potential well of finite depth is presented. The electronic matrix element HBA for thermal electron transfer is calculated using these wave functions, and is compared with values of HBA obtained using the exact solution of the same Schrödinger equation. The present method yields accurate results for HBA, within the oblate spheroidal potential well model, and is useful for examining the orientational effects of the two centers on the rate of electron transfer.