IVR formulation of Miller's correspondence relations

被引:16
作者
Kay, KG [1 ]
机构
[1] Bar Ilan Univ, Dept Chem, IL-52900 Ramat Gan, Israel
关键词
D O I
10.1021/jp0034675
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
The correspondence rules of Miller, determining semiclassical approximations for general quantum amplitudes <X-2/X-1>, are formulated in a way that is analogous to the initial value representation (IVR) treatments of the propagator. The semiclassical formulas obtained in this way do not require numerical searches, are free from caustic singularities, and are often uniform approximations. However, to develop treatments that retain the power and generality of Miller's rules, it is necessary to overcome boundary condition difficulties that arise when the x's are not Cartesian coordinates. Such problems can be solved by replacing Gaussian factors, analogous to those appearing in existing IVR treatments of the propagator, with more general non-Gaussian functions. It is suggested that factors of this kind can be obtained from certain IVR representations for wave functions that are exact for particular model systems. Examples of such factors are presented, and the resulting theory is illustrated. In one application, an IVR expression for the elastic scattering differential cross section that is uniform for all angles is developed and tested.
引用
收藏
页码:2535 / 2545
页数:11
相关论文
共 93 条
[1]  
[Anonymous], 1991, Semiclassical Mechanics with Molecular Applications
[2]  
[Anonymous], 1964, Handbook of mathematical functions
[3]   Semiclassical molecular dynamics simulations of ultrafast photodissociation dynamics associated with the Chappuis band of ozone [J].
Batista, VS ;
Miller, WH .
JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (02) :498-510
[4]   WAVES AND THOMS THEOREM [J].
BERRY, MV .
ADVANCES IN PHYSICS, 1976, 25 (01) :1-26
[5]   SEMICLASSICAL APPROXIMATIONS IN WAVE MECHANICS [J].
BERRY, MV ;
MOUNT, KE .
REPORTS ON PROGRESS IN PHYSICS, 1972, 35 (04) :315-+
[6]   On the scaling of semiclassical initial value methods [J].
Brewer, ML .
JOURNAL OF CHEMICAL PHYSICS, 1999, 111 (14) :6168-6170
[7]   Semiclassical dynamics in up to 15 coupled vibrational degrees of freedom [J].
Brewer, ML ;
Hulme, JS ;
Manolopoulos, DE .
JOURNAL OF CHEMICAL PHYSICS, 1997, 106 (12) :4832-4839
[8]   Semiclassical initial value theory for dissociation dynamics [J].
Campolieti, G ;
Brumer, P .
JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (03) :791-803
[9]   SEMICLASSICAL PROPAGATION - PHASE INDEXES AND THE INITIAL-VALUE FORMALISM [J].
CAMPOLIETI, G ;
BRUMER, P .
PHYSICAL REVIEW A, 1994, 50 (02) :997-1018
[10]   Generalized semiclassical-phase-index formulas via sequential stationary phase [J].
Campolieti, G ;
Brumer, P .
PHYSICAL REVIEW A, 1996, 53 (05) :2958-2970