Transfer reactions of Rydberg (quasi-Rydberg molecular) electrons in condensed media: V. Large proton displacement in the N-H bond upon photoionization of diphenylamine via highly excited triplet state T* in methanol at 77 K

被引:0
作者
Skvortsov, VI [1 ]
机构
[1] Russian Acad Sci, Inst Problems Chem Phys, Chernogolovka 142432, Russia
基金
俄罗斯基础研究基金会;
关键词
Hydrogen; Methanol; Physical Chemistry; Hydrogen Atom; Radical Cation;
D O I
10.1023/A:1014667130456
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The mechanism of large proton displacements in polarized R-Hdelta+ bonds, which involves the formation of a triplet complex R...H* (H* is the excited hydrogen atom) in the T* state upon the capture of an excited pi* electron onto the p, d, and f quasi-Rydberg proton orbitals in Hdelta+ (part IV) is further substantiated. It is assumed that the proton displaced upon photoionization of added diphenylamine molecules (Ph2NH) via the complex Ph2N...H* in methanol at 77 K can be fixed by the polarization of the medium in the vicinity of the diphenylaminyl radical (Ph2N...H-sol(+)) formed. When the solution is thawed up to 106 K, the protons returns to PH2N to afford the radical cation Ph2NH+.
引用
收藏
页码:112 / 115
页数:4
相关论文
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