Electronic Resource
College Park, Md.
:
American Institute of Physics (AIP)
The Journal of Chemical Physics
85 (1986), S. 5041-5044
ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The question of intensity vs energy fluence dependence in the IR excitation of a polyatomic molecule in the quasicontinuum is addressed. It was found that the energy fluence scaling law breaks down for laser pulses shorter than ∼100 ps for C3F7I. This is consistent with similar results obtained previously for SF6 and C2F5Cl. The reason for the increased intensity dependence is physically due to an increase in the intrinsic small signal absorption cross section of the polyatomic molecules for short interaction times. This increase in the absorption coefficient is not intensity related and is a fundamental property of a dense ensemble of interacting states. The change in the absorption cross section for all molecules studied reveals a nonequilibration of energy relaxation among all the states even for 100 ps pulses. This nonequilibrium situation can be exploited to achieve ps nonstatistical photochemistry.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.451694
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