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## Full-Text Articles in Physics

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

*All HMC Faculty Publications and Research*

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 ...

Calculation Of Electronic Coupling Matrix Elements For Ground And Excited State Electron Transfer Reactions: Comparison Of The Generalized Mulliken–Hush And Block Diagonalization Methods, Robert J. Cave, Marshall D. Newton

#### Calculation Of Electronic Coupling Matrix Elements For Ground And Excited State Electron Transfer Reactions: Comparison Of The Generalized Mulliken–Hush And Block Diagonalization Methods, Robert J. Cave, Marshall D. Newton

*All HMC Faculty Publications and Research*

Two independent methods are presented for the nonperturbative calculation of the electronic coupling matrix element (Hab) for electron transfer reactions using ab initio electronic structure theory. The first is based on the generalized Mulliken–Hush (GMH) model, a multistate generalization of the Mulliken Hush formalism for the electronic coupling. The second is based on the block diagonalization (BD) approach of Cederbaum, Domcke, and co-workers. Detailed quantitative comparisons of the two methods are carried out based on results for (a) several states of the system Zn2OH2+ and (b) the low-lying states of the benzene–Cl atom complex and its contact ion ...

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 *H*_{BA} for thermal electron transfer is calculated using these wave functions, and is compared with values of *H*_{BA} obtained using the exact solution of the same Schrödinger equation. The present method yields accurate results for *H*_{BA}, 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.

A Model For Orientation Effects In Electron‐Transfer Reactions, Paul Siders, Robert J. Cave, R.A. Marcus

#### A Model For Orientation Effects In Electron‐Transfer Reactions, Paul Siders, Robert J. Cave, R.A. Marcus

*All HMC Faculty Publications and Research*

A method for solving the single‐particle Schrödinger equation with an oblate spheroidal potential of finite depth is presented. The wave functions are then used to calculate the matrix element *T*_{BA} which appears in theories of nonadiabatic electron transfer. The results illustrate the effects of mutual orientation and separation of the two centers on *T*_{BA}. Trends in these results are discussed in terms of geometrical and nodal structure effects. Analytical expressions related to *T*_{BA} for states of spherical wells are presented and used to analyze the nodal structure effects for *T*_{BA} for the spheroidal wells.