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


Journal Article

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.

Full Text

Cited Authors

  • Migliore, A; Corni, S; Di Felice, R; Molinari, E

Published Date

  • February 2006

Published In

Volume / Issue

  • 124 / 6

Start / End Page

  • 64501 -

PubMed ID

  • 16483214

Pubmed Central ID

  • 16483214

Electronic International Standard Serial Number (EISSN)

  • 1089-7690

International Standard Serial Number (ISSN)

  • 0021-9606

Digital Object Identifier (DOI)

  • 10.1063/1.2166233


  • eng