An adiabatic linearized path integral approach for quantum time functions: Electronic transport in metal-molten salt solutions

被引:22
作者
Causo, MS
Ciccotti, G
Montemayor, D
Bonella, S
Coker, DF [1 ]
机构
[1] Boston Univ, Dept Chem, 590 Commonwealth Ave, Boston, MA 02215 USA
[2] Univ Roma La Sapienza, Dipartimento Fis, I-00185 Rome, Italy
关键词
D O I
10.1021/jp045208b
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
We generalize the linearized path integral approach to evaluate quantum time correlation functions for systems best described by a set of nuclear and electronic degrees of freedom, restricting ourselves to the adiabatic approximation. If the operators in the correlation function are nondiagonal in the electronic states, then this adiabatic linearized path integral approximation for the thermal averaged quantum dynamics presents interesting and distinctive features, which we derive and explore in this paper. The capability of these approximations to accurately reproduce the behavior of physical systems is demonstrated by calculating the diffusion constant for an excess electron in a metal-molten salt solution.
引用
收藏
页码:6855 / 6865
页数:11
相关论文
共 30 条
[1]  
ALARVI A, COMMUNICATION
[2]  
BONELLA S, IN PRESS COMPUT PHYS
[3]  
BREDIG MA, 1964, MOLTEN SALT CHEM
[4]   Wigner approach to the semiclassical dynamics of a quantum many-body system:: the dynamic scattering function of 4He [J].
Ciccotti, G ;
Pierleoni, C ;
Capuani, F ;
Filinov, VS .
COMPUTER PHYSICS COMMUNICATIONS, 1999, 121 :452-459
[5]   APPROACH TO METALLIC BEHAVIOR IN METAL MOLTEN-SALT SOLUTIONS [J].
FOIS, E ;
SELLONI, A ;
PARRINELLO, M .
PHYSICAL REVIEW B, 1989, 39 (07) :4812-4815
[6]   BIPOLARONS IN METAL METAL HALIDE SOLUTIONS [J].
FOIS, ES ;
SELLONI, A ;
PARRINELLO, M ;
CAR, R .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (11) :3268-3273
[7]   OPTICAL STUDY OF ELECTRON LOCALIZATION APPROACHING A POLARIZATION CATASTROPHE IN LIQUID KX-KCL1-X [J].
FREYLAND, W ;
GARBADE, K ;
PFEIFFER, E .
PHYSICAL REVIEW LETTERS, 1983, 51 (14) :1304-1306
[8]   TRANSPORT COEFFICIENTS FROM DISSIPATION IN A CANONICAL ENSEMBLE [J].
HELFAND, E .
PHYSICAL REVIEW, 1960, 119 (01) :1-9
[9]   Quantum time correlation functions and classical coherence [J].
Hernandez, R ;
Voth, GA .
CHEMICAL PHYSICS, 1998, 233 (2-3) :243-255
[10]   FLUCTUATION-DISSIPATION THEOREM [J].
KUBO, R .
REPORTS ON PROGRESS IN PHYSICS, 1966, 29 :255-+