Vibrational population relaxation

Oxtoby D W 1981 Vibrational population relaxation in liquids Photoselective Chemistry Part 2 (Advances in Chemical Physics 47) ed J Jortner, R D Levine and S A Rise (New York Wiley) pp 487-519... 

Jiang Y J and B G 1994 Vibrational population relaxation of perylene in its ground and exoited eleotronio states J. Phys. Chem. 98 9417-21... 

If the system under consideration is chemically inert, the laser excitation only induces heat, accompanied by density and pressure waves. The excitation can be in the visible spectral region, but infrared pumping is also possible. In the latter case, the times governing the delivery of heat to the liquid are those of vibrational population relaxation. They are very short, on the order of 1 ps this sort of excitation is thus impulsive. Contrary to a first impression, the physical reality is in fact quite subtle. The acoustic horizon, described in Section VC is at the center of the discussion [18, 19]. As laser-induced perturbations cannot propagate faster than sound, thermal expansion is delayed at short times. The physicochemical consequences of this delay are still entirely unknown. The liquids submitted to investigation are water and methanol. 

The Molecular Mechanisms Behind the Vibrational Population Relaxation of Small Molecules in Liquids... 

Oxtoby DW. Vibrational population relaxation in liquids. In Jortner J, Levine RD, Rice SA, eds. Photoselective Chemistry Part 2. Vol. 47. New York Wiley, 1981 487-519. 

Vibrational population relaxation plays a fundamental role in many physical and chemical processes in liquids. In liquid-state photochemical reactions there is often competition between relaxation and reaction and the observed reaction rates and yields can therefore be quite sensitive to solute-solvent interactions. There has also been considerable recent interest in the possible development of liquid state chemical lasers based on the long vibrational lifetimes observed in simple liquids. For both these prob-... 

In this chapter we review experimental and theoretical studies of vibrational population relaxation in liquids. This review is complementary to our previous article in the same series, which treated vibrational phase relaxation (dephasing) in liquids due to vibrationally elastic interactions. A number of reviews have appeared recently on related subjects vibrational relaxation in solid matrices has been covered elsewhere, and several reviews have been devoted to experimental studies of picosecond time-scale relaxation processes in liquids. Diestler has recently reviewed theoretical studies of vibrational relaxation in liquids and solids the focus of the present article is rather different from that of Diestler. 

In order to stndy the short time vibrational energy transfer behavior of a vibra-tionally excited system, we employ a non-Markovian time-dependent perturbation theory [83]. Onr approach builds on the successful application of Markovian time-dependent pertnrbation theory by Leitner and coworkers to explore heat flow in proteins and glasses, and Tokmakoff, Payer, and others, in modeling vibrational population relaxation of selected modes in larger molecules. In a separate chapter in this volnme, Leitner provides an overview of the development of normal mode-based methods, snch as the one employed here, for the study of energy flow in solids and larger molecnlar systems. 

Sagnella, D. E. Straub, J. E. Jackson, T. A. Lim, M. Anfinrud, P. A., Vibrational population relaxation of carbon monoxide in the heme pocket of photolyzed carhonmonoxy myoglobin Comparison of time-resolved mid-lR absorbance experiments and molecular dynamics simulations. Proc. Natl. Acad. Sci. U. S. A. 1999, 96, 14324—14329. 

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