Computing the superexchange electronic factor of electron transfer theory using a grid-based numerical method Academic Article

abstract

• We report a method for calculating the electronic factor in the superexchange rate equation of electron transfer theory; this method is a basis set independent, grid-based numerical technique that utilizes fast Fourier transforms (FFTs) and a Lanczos recursion in a pseudospectral framework and is used to treat a three-dimensional one-electron model of the electronic factor. We compare eigenvalues calculated from the current method to eigenvalues from the literature for both one-dimensional (ID) and three-dimensional (3D) model problems and find that the current method provides excellent accuracy and efficiency. With respect to the superexchange electronic factor, we use model potentials to calculate the tunneling matrix elements with the present method to illustrate how the method can be used to address current issues in superexchange. In particular, we show how this method is useful in evaluating the effect of the bridge potential on the superexchange electronic factor when using repulsive-core pseudopotentials to represent the bridge. 2000 John Wiley & Sons, Inc.

authors

• Lucchese, Robert

published proceedings

• JOURNAL OF COMPUTATIONAL CHEMISTRY

author list (cited authors)

• Wells, M. C., & Lucchese, R. R.

citation count

• 1

complete list of authors

• Wells, MC||Lucchese, RR

publication date

• November 2000

publisher

• Wiley  Publisher

published in

• Journal of Computational Chemistry  Journal

keywords

• Electron Transfer
• Electronic Factor
• Fast Fourier Transforms
• Lanczos Diagonalization
• Superexchange

Digital Object Identifier (DOI)

• 10.1002/1096-987X(20001115)21:14<1262::AID-JCC5>3.0.CO;2-H

start page

• 1262

end page

• 1273

volume

• 21

issue

• 14

URL

• http://dx.doi.org/10.1002/1096-987x(20001115)21:14%3C1262::aid-jcc5%3E3.0.co;2-h