Hrp versus Vrp in NWChem

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9:32:33 AM PDT - Tue, Oct 23rd 2012
WITH regard to the electron transfer part in http://nwchemgit.github.io/index.php/Release61:Electron_Transfer, according to the paper "A. Farazdel, M. Dupuis, E. Clementi, and A. Aviram, J. Am. Chem. Soc., 112, 4206 (1990)": Hrp is the "electronic coupling matrix element" Vrp is the "electron transfer matrix element", Vrp can be calculated from Hrp, and only in the limit of small Srp, Vrp=Hrp in most papers the parameter used in Marcus equation is Hrp, electronic coupling matrix element. But the one provided by NWChem seems to be Vrp, electron transfer matrix element. Moreover, from the example provided by NWChem, the difference between Vrp and Hrp is huge. Which one should be used in Marcus equation?

Forum Vet

4:42:57 PM PDT - Fri, Oct 26th 2012
As is outlined in the paper you quoted, Vrp is the parameter to be used in the Marcusequation. Bert Quote:Tiechong Oct 23rd 4:32 pm WITH regard to the electron transfer part in http://nwchemgit.github.io/index.php/Release61:Electron_Transfer, according to the paper "A. Farazdel, M. Dupuis, E. Clementi, and A. Aviram, J. Am. Chem. Soc., 112, 4206 (1990)": Hrp is the "electronic coupling matrix element" Vrp is the "electron transfer matrix element", Vrp can be calculated from Hrp, and only in the limit of small Srp, Vrp=Hrp in most papers the parameter used in Marcus equation is Hrp, electronic coupling matrix element. But the one provided by NWChem seems to be Vrp, electron transfer matrix element. Moreover, from the example provided by NWChem, the difference between Vrp and Hrp is huge. Which one should be used in Marcus equation?