Effects of solute electronic structure variation on photon echo spectroscopy

被引:22
作者
Bursulaya, BD [1 ]
Kim, HJ [1 ]
机构
[1] CARNEGIE MELLON UNIV,DEPT CHEM,PITTSBURGH,PA 15213
关键词
D O I
10.1021/jp961001+
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Two-pulse photon echo spectroscopy for dipolar solutes in water is studied via equilibrium and nonequilibrium molecular dynamics (MD) simulations, By extension of the valence-bond description employed in our earlier MD work [Bursulaya, B. D.; Zichi, D. A.; Kim, H. J. J. Phys. Chem. 1995, 99, 10069; 1996, 100, 1392], both the solute ground- and excited-state electronic polarizabilities are incorporated into the simulations. By modulation of the static transition frequency distribution and solvation dynamics, the state-dependent solute electronic structure variation is found to have a significant influence on the echo; its relaxation behavior with pulse delay is slower for a polarizable solute than for a nonpolarizable one. Despite their similar overall effects, however, the ground- and excited-state polarizabilities modulate the echo via rather different mechanisms, Equilibrium and nonequilibrium MD yields similar results for a nonpolarizable solute but discernible differences for a polarizable solute.
引用
收藏
页码:16451 / 16456
页数:6
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