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.

First-principles DFT calculations of Electron Transfer rates in Azurin Dimers / Migliore, Agostino; S., Corni; DI FELICE, Rosa; Molinari, Elisa. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - STAMPA. - 124:(2006), pp. 064501-064501.

First-principles DFT calculations of Electron Transfer rates in Azurin Dimers

MIGLIORE, Agostino;DI FELICE, ROSA;MOLINARI, Elisa
2006

Abstract

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.
2006
124
064501
064501
First-principles DFT calculations of Electron Transfer rates in Azurin Dimers / Migliore, Agostino; S., Corni; DI FELICE, Rosa; Molinari, Elisa. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - STAMPA. - 124:(2006), pp. 064501-064501.
Migliore, Agostino; S., Corni; DI FELICE, Rosa; Molinari, Elisa
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/455019
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact