Quantum energy flow during molecular isomerization

被引:87
作者
Leitner, DM [1 ]
Wolynes, PG [1 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
关键词
D O I
10.1016/S0009-2614(97)01120-2
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
Intramolecular energy flow greatly influences molecular isomerizations, particularly when the energy barrier to reaction is low, as in catalytic and biochemical reactions. We discuss here a simple quantum mechanical theory that describes the extent and rate of vibrational energy flow in molecules, and apply it for the first time to predict rates of isomerization. We consider trans-cis photoisomerization of stilbene, which has been extensively studied experimentally. Vibrational flow in stilbene plays a crucial role in moderating isomerization; the rate both in supersonic jets and low pressure gases is well described by the theory treating quantum flow. (C) 1997 Elsevier Science B.V.
引用
收藏
页码:411 / 418
页数:8
相关论文
共 39 条
[1]   UNIMOLECULAR REACTIONS IN ISOLATED AND COLLISIONAL SYSTEMS - IS THE TRANSITION-STATE RATE AN UPPER LIMIT FOR THE ISOMERIZATION OF STILBENE [J].
BALK, MW ;
FLEMING, GR .
JOURNAL OF PHYSICAL CHEMISTRY, 1986, 90 (17) :3975-3983
[2]   Femtosecond real-time probing of reactions .20. Dynamics of twisting, alignment, and IVR in the trans-stilbene isomerization reaction [J].
Baskin, JS ;
Banares, L ;
Pedersen, S ;
Zewail, AH .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (29) :11920-11933
[3]   CLASSICAL AND MODERN METHODS IN REACTION-RATE THEORY [J].
BERNE, BJ ;
BORKOVEC, M ;
STRAUB, JE .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (13) :3711-3725
[4]   A SIMPLE MATRIX MODEL OF INTRAMOLECULAR VIBRATIONAL REDISTRIBUTION AND ITS IMPLICATIONS [J].
BIGWOOD, R ;
GRUEBELE, M .
CHEMICAL PHYSICS LETTERS, 1995, 235 (5-6) :604-613
[5]   Classical trajectory study of collision induced intramolecular energy transfer in trans-stilbene [J].
Bolton, K ;
Nordholm, S .
CHEMICAL PHYSICS, 1996, 206 (1-2) :103-128
[6]   A classical molecular dynamics study of the intramolecular energy transfer of model trans-stilbene [J].
Bolton, K ;
Nordholm, S .
CHEMICAL PHYSICS, 1996, 203 (01) :101-126
[7]   Beats in internal vibrational energy redistribution in trans-stilbene - A study of the quantum and classical correspondence [J].
Bolton, K ;
Nordholm, S .
CHEMICAL PHYSICS, 1996, 207 (01) :63-76
[8]   UNIMOLECULAR REACTIONS IN ISOLATED AND COLLISIONAL SYSTEMS - DEUTERIUM-ISOTOPE EFFECT IN THE PHOTOISOMERIZATION OF STILBENE [J].
COURTNEY, SH ;
BALK, MW ;
PHILIPS, LA ;
WEBB, SP ;
YANG, D ;
LEVY, DH ;
FLEMING, GR .
JOURNAL OF CHEMICAL PHYSICS, 1988, 89 (11) :6697-6707
[9]   PHOTOISOMERIZATION OF STILBENE IN LOW VISCOSITY SOLVENTS - COMPARISON OF ISOLATED AND SOLVATED MOLECULES [J].
COURTNEY, SH ;
FLEMING, GR .
JOURNAL OF CHEMICAL PHYSICS, 1985, 83 (01) :215-222
[10]   RATES OF PHOTOISOMERIZATION OF TRANS-STILBENE IN ISOLATED AND SOLVATED MOLECULES - EXPERIMENTS ON THE DEUTERIUM-ISOTOPE EFFECT AND RRKM BEHAVIOR [J].
FELKER, PM ;
ZEWAIL, AH .
JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (25) :5402-5411