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Calculation of electron-transfer matrix elements of bridged systems using a molecular fragment approach

Siddarth, Prabha and Marcus, R. A. (1992) Calculation of electron-transfer matrix elements of bridged systems using a molecular fragment approach. Journal of Physical Chemistry, 96 (8). pp. 3213-3217. ISSN 0022-3654. doi:10.1021/j100187a008. https://resolver.caltech.edu/CaltechAUTHORS:20150514-155515321

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Abstract

A perturbation method for calculating the electronic coupling for electron-transfer reactions between a donor and an acceptor separated by large or small bridges is developed. In this approach the intervening bridge is subdivided into smaller molecular fragments, thereby enabling calculations on larger systems. This method of molecular fragments is tested for a series of polyproline bridged systems. The results obtained for the electron transfer matrix element are compared with those obtained from direct diagonalization of the full bridge and with experimental results. Previously, the result for the direct diagonalization of the bridge had been shown to agree with that obtained from diagonalization of the entire donor bridge-acceptor system. The vertical donor-bridge orbital energy difference is estimated with the aid of a donor bridge charge-transfer spectrum.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/j100187a008DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100187a008PublisherArticle
ORCID:
AuthorORCID
Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1992 American Chemical Society. Received August 23, 1991; In Final Form December 20, 1991. It is a pleasure to acknowledge the support of this research by the Office of Naval Research and the National Science Foundation. We are particularly indebted to Norman Sutin for his very helpful and perceptive comments and to Jim Wishart for providing us with information on the charge-transfer spectra.
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Office of Naval Research (ONR)UNSPECIFIED
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Caltech Noyes Laboratory of Chemical Physics8490
Issue or Number:8
DOI:10.1021/j100187a008
Record Number:CaltechAUTHORS:20150514-155515321
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150514-155515321
Official Citation:Siddarth, P., & Marcus, R. A. (1992). Calculation of electron-transfer matrix elements of bridged systems using a molecular fragment approach. The Journal of Physical Chemistry, 96(8), 3213-3217. doi: 10.1021/j100187a008
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:57547
Collection:CaltechAUTHORS
Deposited By: Joanne McCole
Deposited On:14 May 2015 23:26
Last Modified:10 Nov 2021 21:51

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