FULL-DIMENSIONAL TIME-DEPENDENT TREATMENT FOR DIATOM-DIATOM REACTIONS - THE H-2+OH REACTION

被引:458
作者
ZHANG, DH
ZHANG, JZH
机构
[1] Department of Chemistry, New York University, New York
关键词
D O I
10.1063/1.467808
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
Extending our previous studies for the H-2+OH reaction in five mathematical dimensions (5D) [J. Chem. Phys. 99, 5615 (1993); 100, 2697 (1994)], we present in this; paper a full-dimensional (6D) dynamics study for the title reaction. The 6D treatment uses the time-dependent wave-packet approach and employs discrete variable representations for three radial coordinates and coupled angular momentum basis functions for three angular coordinates. The present 6D study employs an energy projection method to extract reaction probabilities for a whole range of energies from a single wave-packet propagation, while previous studies produced only energy-averaged reaction probability from a single wave-packet propagation. The application of the energy-projection method allows us to efficiently map out the energy dependence of the reaction probability on a fine grid which revealed surprisingly sharp resonancelike features at low collision energies on the Schatz-Elgersma potential surface. Our calculation shows that the potential-averaged 5D treatment can produce reaction probabilities essentially indistinguishable from the full-dimensional result. We also report initial state-selected reaction cross sections and rate constants which are in good agreement with our previous calculations. The effect of OH vibration on H-2+OH reaction is examined in the present study and our calculation shows that the OH vibration can enhance the rate constant by about a factor of 1.7 in good agreement with the experimental estimate of about 1.5.
引用
收藏
页码:1146 / 1156
页数:11
相关论文
共 86 条
[51]   A TIME-DEPENDENT WAVE PACKET APPROACH TO ATOM DIATOM REACTIVE COLLISION PROBABILITIES - THEORY AND APPLICATION TO THE H+H-2 (J=O) SYSTEM [J].
NEUHAUSER, D ;
BAER, M ;
JUDSON, RS ;
KOURI, DJ .
JOURNAL OF CHEMICAL PHYSICS, 1990, 93 (01) :312-322
[52]   THE APPLICATION OF WAVE-PACKETS TO REACTIVE ATOM-DIATOM SYSTEMS - A NEW APPROACH [J].
NEUHAUSER, D ;
BAER, M .
JOURNAL OF CHEMICAL PHYSICS, 1989, 91 (08) :4651-4657
[53]  
NEUHAUSER DJ, IN PRESS J CHEM PHYS
[54]   QUANTUM SCATTERING CALCULATIONS ON H2O+H-]H2+OH AND ISOTOPES - ROTATIONAL DISTRIBUTIONS AND CROSS-SECTIONS [J].
NYMAN, G ;
CLARY, DC .
JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (10) :7774-7786
[55]   KINETIC-STUDY OF THE OH+H-2 REACTION FROM 800-K TO 1550-K [J].
OLDENBERG, RC ;
LOGE, GW ;
HARRADINE, DM ;
WINN, KR .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (21) :8426-8430
[56]   SPACE-FIXED VS BODY-FIXED AXES IN ATOM-DIATOMIC MOLECULE SCATTERING - SUDDEN APPROXIMATIONS [J].
PACK, RT .
JOURNAL OF CHEMICAL PHYSICS, 1974, 60 (02) :633-639
[57]   A MOLECULAR-DYNAMICS STUDY OF THE REACTION H2+OH-]H2O+H [J].
RASHED, O ;
BROWN, NJ .
JOURNAL OF CHEMICAL PHYSICS, 1985, 82 (12) :5506-5518
[58]   KINETIC-STUDY OF THE REACTION OF OH WITH H-2 AND D2 FROM 250-K TO 1050-K [J].
RAVISHANKARA, AR ;
NICOVICH, JM ;
THOMPSON, RL ;
TULLY, FP .
JOURNAL OF PHYSICAL CHEMISTRY, 1981, 85 (17) :2498-2503
[59]  
ROSE ME, 1957, ELEMENTARY THEORY AN
[60]   A QUASICLASSICAL TRAJECTORY STUDY OF THE STATE-TO-STATE DYNAMICS OF H+H2O-]OH+H2 [J].
SCHATZ, GC ;
COLTON, MC ;
GRANT, JL .
JOURNAL OF PHYSICAL CHEMISTRY, 1984, 88 (14) :2971-2977