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## Full-Text Articles in Physics

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 ...

Theoretical Studies Of Electron Transfer In Metal Dimers: Xy+→X+Y, Where X, Y=Be, Mg, Ca, Zn, Cd, Robert J. Cave, David V. Baxter, William A. Goddard Iii, John D. Baldeschwieler

#### Theoretical Studies Of Electron Transfer In Metal Dimers: Xy+→X+Y, Where X, Y=Be, Mg, Ca, Zn, Cd, Robert J. Cave, David V. Baxter, William A. Goddard Iii, John D. Baldeschwieler

*All HMC Faculty Publications and Research*

The electronic matrix element responsible for electron exchange in a series of metal dimers was calculated using *a**b* *i**n**i**t**i**o* wave functions. The distance dependence is approximately exponential for a large range of internuclear separations. A localized description, where the two nonorthogonal structures characterizing the electron localized at the left and right sites are each obtained self‐consistently, is found to provide the best description of the electron exchange process. We find that Gaussian basis sets are capable of predicting the expected exponential decay of the electronic interactions even at quite large internuclear distances.

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

*All HMC Faculty Publications and Research*

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.