Abstract
A theoretical description of stimulated-emission pumping with femtosecond laser pulses on complex absorption bands of polyatomic molecules is developed. The strong non-Born-Oppenheimer coupling associated with conical intersections of multidimensional excited-state potential-energy surfaces is included in a fully microscopic manner for appropriate model systems. Additional relaxation effects in the excited-state manifold (lifetime broadening and pure dephasing) are included in the usual phenomenological manner by using the densitymatrix formalism. The calculation of the stimulated-emission pump-probe signalby means of density-matrix perturbation theory is briefly discussed and numerically realized using a time-dependent eigenstate-free treatment of the intramolecular dynamics. Someresults obtained for a simple model of the SI-S2 conical intersection in pyrazine are presented.
Original language | English |
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Pages (from-to) | 1970-1980 |
Number of pages | 11 |
Journal | Journal of the Optical Society of America B: Optical Physics |
Volume | 7 |
Issue number | 9 |
DOIs | |
State | Published - Sep 1990 |