First-principles density-functional theory calculations of electron-transfer rates in azurin dimers

We have conceived and implemented a new method to calculate transfer integrals between molecular sites, which exploits few quantities derived from density-functional theory electronic structure computations and does not require the knowledge of the exact transition state coordinate. The method uses...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 2006-02, Vol.124 (6), p.064501-064501-16
Main Authors: Migliore, A., Corni, S., Di Felice, R., Molinari, E.
Format: Article
Language:English
Subjects:
Algorithms
Azurin - chemistry
Cations, Divalent
Computer Simulation
Copper - chemistry
Dimerization
Electron Transport
Kinetics
Models, Molecular
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:We have conceived and implemented a new method to calculate transfer integrals between molecular sites, which exploits few quantities derived from density-functional theory electronic structure computations and does not require the knowledge of the exact transition state coordinate. The method uses a complete multielectron scheme, thus including electronic relaxation effects. Moreover, it makes no use of empirical parameters. The computed electronic couplings can then be combined with estimates of the reorganization energy to evaluate electron-transfer rates that are measured in kinetic experiments: the latter are the basis to interpret electron-transfer mechanisms. We have applied our approach to the study of the electron self-exchange reaction of azurin, an electron-transfer protein belonging to the family of cupredoxins. The transfer integral estimates provided by the proposed method have been compared with those resulting from other computational techniques, from empirical models, and with available experimental data.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.2166233