title: Effect of group electronegativity on electron transfer in bis(hydrazine) radical cations.
abstract: The radical cation of 4,10-ditert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2]-tetradecane (sBI4T(+)), as well as its substituted bis(hydrazine) radical cations, is chosen for the investigation of the electronegativity dependence of its intramolecular electron transfer. To do so, two parameters, reorganization energy and electronic coupling, are calculated with several ab initio approaches. It is found that the electronic couplings decrease with the increase of the group electronegativity while the reorganization energies do not show an explicit dependency. Furthermore, Marcus formula is employed to reveal those effect on the electron transfer rates. The predicted rates of electron transfer generally decrease with increasing group electronegativity, although not monotonically.
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, People's Republic of China.
authors.forename: Haimei
authors.initials: H
authors.lastname: Qin
authors.forename: Xinxin
authors.initials: X
authors.lastname: Zhong
authors.forename: Yubing
authors.initials: Y
authors.lastname: Si
authors.forename: Weiwei
authors.initials: W
authors.lastname: Zhang
authors.forename: Yi
authors.initials: Y
authors.lastname: Zhao
mesh_terms: D002412:Cations / Q000737:chemistry; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry; D006834:Hydrazines / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D002412:Cations; D005609:Free Radicals; D006834:Hydrazines