A time-dependent discrete variable representation method

被引:50
作者
Adhikari, S [1 ]
Billing, GD [1 ]
机构
[1] Univ Copenhagen, HC Orsted Inst, Dept Chem, DK-2100 Copenhagen O, Denmark
关键词
D O I
10.1063/1.481959
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 have developed a novel discrete variable representation (DVR) method where not only the amplitudes of the wave function at the DVR grid points can change but also the positions of these grid points can move as a function of time. Since the Gauss-Hermite basis set is used as the primitive basis functions (PBF) to construct the DVR basis set, the method appears as a semiclassical one with a small number of PBF but converges very fast to the quantum with an increasing PBF. We have investigated the dynamics of a reaction coordinate with or without coupling to a heat bath of harmonic oscillators to demonstrate the validity of the proposed method. The excellent agreement of the calculated tunneling probabilities with numbers obtained by traditional quantum grid method (FFT) and the fast computability of the present method compared to the latter are remarkable. (C) 2000 American Institute of Physics. [S0021-9606(00)30113-1].
引用
收藏
页码:1409 / 1414
页数:6
相关论文
共 23 条
[1]   Semiclassical reactive scattering: the Hermite correction method in hyperspherical coordinates [J].
Adhikari, S ;
Billing, GD .
CHEMICAL PHYSICS, 1998, 238 (01) :69-84
[2]   The Hermite correction method for nonadiabatic transitions [J].
Adhikari, S ;
Billing, GD .
JOURNAL OF CHEMICAL PHYSICS, 1999, 111 (01) :48-53
[3]   The Gauss-Hermite basis set in a tunneling problem [J].
Adhikari, S ;
Billing, GD .
CHEMICAL PHYSICS LETTERS, 1999, 309 (3-4) :249-256
[4]   Hermits correction method in hyperspherical coordinates: Application to chemical reactions [J].
Adhikari, S ;
Billing, GD .
CHEMICAL PHYSICS LETTERS, 1999, 305 (1-2) :109-116
[5]   THEORETICAL METHODS FOR ROVIBRATIONAL STATES OF FLOPPY MOLECULES [J].
BACIC, Z ;
LIGHT, JC .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1989, 40 :469-498
[6]  
Billing G. D, 1998, ENCY COMPUTATIONAL C
[7]   THE IMPROVEMENT OF THE TDSCF METHOD FOR A REACTION COORDINATE COUPLED TO A HEAT BATH [J].
BILLING, GD ;
JOLICARD, G .
CHEMICAL PHYSICS LETTERS, 1994, 221 (1-2) :75-80
[8]   Quantum corrections to the classical path equations: Multitrajectory and Hermite corrections [J].
Billing, GD .
JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (11) :4286-4294
[9]   EXTENDED WAVE PACKET DYNAMICS - EXACT SOLUTION FOR COLLINEAR ATOM, DIATOMIC MOLECULE-SCATTERING [J].
COALSON, RD ;
KARPLUS, M .
CHEMICAL PHYSICS LETTERS, 1982, 90 (04) :301-305
[10]   A NOVEL DISCRETE VARIABLE REPRESENTATION FOR QUANTUM-MECHANICAL REACTIVE SCATTERING VIA THE S-MATRIX KOHN METHOD [J].
COLBERT, DT ;
MILLER, WH .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (03) :1982-1991