Journal of the Serbian Chemical Society 2013 Volume 78, Issue 1, Pages: 65-73
https://doi.org/10.2298/JSC120618066E
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Effect of temperature on rate of the spin-forbidden transition in uracil and thymine
Etinski Mihajlo (Faculty of Physical Chemistry, Belgrade)
The intersystem crossing rates of uracil and thymine molecules in interaction
with the heat bath were studied by means of the ab initio methods. The rates
were calculated employing the time-dependent approach based on the
correlation function. The normal modes of the singlet and triplet electronic
states were related by the Duschinsky transformation. The correlation
function was calculated using the Condon approximation for the spin-orbit
matrix element and harmonic approximation for the nuclear motion. The excess
vibrational energy in the initial singlet excited electronic state decreases
the rate of the triplet formation in uracil and thymine. This decrease is
more pronounced for uracil. Also, it was found that the change of the
adiabatic energy gap can significantly modify the rate of the triplet
formation.
Keywords: excited states, intersystem crossing, correlation function