Theoretical and computational studies of solvent and vibrational dynamic effects on electron transfer reactions and overtone vibrational dephasing in liquids
Abstract
This thesis consists of two parts. In the first part, a detailed theoretical study of
the effects of ultrafast polar solvent modes and the intramolecular vibrational modes
on electron transfer reaction (E T R ) is presented. The same study highlights the role
of high-frequency vibrational modes on E T R in the Marcus inverted regime. In the
second part of the thesis, a detailed study of solvent effects on overtone vibrational
dephasing carried out to investigate the subquadratic quantum number dependence
of the dephasing rate. This part itself consists of two separate investigations. In the
first half of part II, an analytical treatment of the vibrational dephasing problem
is presented. This is based on the mode-coupling theory (MCT) to calculate the
time correlation functions of the force on the vibrational coordinate in order to
understand the subquadratic quantum number dependence of overtone vibrational
dephasing. In the second half of part II, a molecular dynamics simulation study of
two different systems carried out to check the theoretical predictions is presented