Recent developments in radiationless transitions
Journal
Progress in Chemistry
Journal Volume
24
Journal Issue
6
Pages
928-949
Date Issued
2012
Author(s)
Abstract
In this paper, we introduce recent works on the mathematical treatments and the first-principle calculations concerning the internal conversion rates for the cases with anharmonic potentials, and conical intersecting potentials. The simulations of absorption and emission spectra with anharmonic effects are also presented to check the validity of the potential energy surfaces obtained from the quantum chemical calculations. The effect of conical intersection on internal conversion has attracted considerable attention. In this paper a different approach is proposed and applied to pyrazine. Another important non-radiative process, molecular vibrational relaxation, is also treated by applying the adiabatic approximation to the ab initio anharmonic potential energy surfaces. The vibrational relaxation rates in water dimer and aniline are chosen to demonstrate the calculation.
Subjects
Anharmonic effect; Double well potential; Internal conversion; Radiationless transition; Vibrational relaxation
Type
journal article