Ab initio calculations on the intramolecular electron transfer rates of a bis(hydrazine) radical cation.
Electron transfer (ET) rates of a charge localized (Class II) intervalence radical cation of a bis(hydrazine) are investigated theoretically. First, the intramolecular ET parameters, i.e., reorganization energy, electronic coupling, and effective frequency, are calculated using several ab initio approaches. And then, the extended Sumi-Marcus theory is employed to predict ET rates by using the parameters obtained. The results reveal that the rates of three isomers of [22/hex/22]+, oo+[22/hex/22]+, io +[22/hex/22]+, and oi+[22/hex/22]+, are agreement with the experiment quite well while the rate of isomer ii+[22/hex/22]+ is about 1000 times larger than those of the others. The validity of different ab initio approaches for this system is discussed.
Zhang
Weiwei
W
Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, P R China.
Zhu
Wenjuan
W
Liang
Wanzhen
W
Zhao
Yi
Y
Nelsen
Stephen F
SF