Relative efficacy of vibrational vs. translational excitation in promoting atom-diatom reactivity: Rigorous examination of Polanyi's rules and proposition of sudden vector projection (SVP) model

被引:179
作者
Jiang, Bin [1 ]
Guo, Hua [1 ]
机构
[1] Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA
基金
美国国家科学基金会;
关键词
POTENTIAL-ENERGY SURFACE; BORN-OPPENHEIMER APPROXIMATION; QUANTIZED TRANSITION-STATES; SPIN-ORBIT REACTIVITY; QUANTUM WAVE-PACKET; CHEMICAL-REACTIONS; REACTION DYNAMICS; CHLORINE ATOM; REACTION-PATH; BIMOLECULAR REACTIONS;
D O I
10.1063/1.4810007
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
To provide a systematic and rigorous re-examination of the well-known Polanyi's rules, excitation functions of several A + BC(nu = 0, 1) reactions are determined using the Chebyshev real wave packet method on accurate potential energy surfaces. Reactions with early (F + H-2 and F + HCl), late (Cl + H-2), and central (H/D/Mu + H-2, where Mu is a short-lived light isotope of H) barriers are represented. Although Polanyi's rules are in general consistent with the quantum dynamical results, their predictions are strictly valid only in certain energy ranges divided by a cross-over point. In particular, vibrational excitation of the diatomic reactant typically enhances reactivity more effectively than translational excitation at high energies, while reverse is true at low energies. This feature persists irrespective of the barrier location. A sudden vector projection model is proposed as an alternative to Polanyi's rules. It is found to give similar, but more quantitative, predictions about mode selectivity in these reactions, and has the advantage to be extendible to reactions involving polyatomic molecules. (C) 2013 AIP Publishing LLC.
引用
收藏
页数:10
相关论文
共 79 条
[1]   Theoretical study of the validity of the Born-Oppenheimer approximation in the Cl+H2→HCl+H reaction [J].
Alexander, MH ;
Capecchi, G ;
Werner, HJ .
SCIENCE, 2002, 296 (5568) :715-718
[2]   Quantum scattering calculations on chemical reactions [J].
Althorpe, SC ;
Clary, DC .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 2003, 54 :493-529
[3]   RATES OF ENDOTHERMIC REACTIONS HCL plus X(X=I,CL) AS A FUNCTION OF REAGENT VIBRATION, ROTATION, AND TRANSLATION [J].
ANLAUF, KG ;
MAYLOTTE, DH ;
POLANYI, JC ;
BERNSTEIN, RB .
JOURNAL OF CHEMICAL PHYSICS, 1969, 51 (12) :5716-+
[4]  
[Anonymous], 2007, POLYRATE 9 7
[5]   The H+H2 reactive system.: Progress in the study of the dynamics of the simplest reaction [J].
Aoiz, FJ ;
Bañares, L ;
Herrero, VJ .
INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY, 2005, 24 (01) :119-190
[6]   EFFECTS OF TRANSLATIONAL, ROTATIONAL, AND VIBRATIONAL-ENERGY ON THE DYNAMICS OF THE D+H2 EXCHANGE-REACTION - A CLASSICAL TRAJECTORY STUDY [J].
AOIZ, FJ ;
HERRERO, VJ ;
RABANOS, VS .
JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (12) :7991-8007
[7]   QUASICLASSICAL TRAJECTORY STUDIES OF THE H+H2 REACTION ON AN ACCURATE POTENTIAL-ENERGY SURFACE .2. EFFECT OF INITIAL VIBRATION AND ROTATION ON REACTIVITY [J].
BARG, GD ;
MAYNE, HR ;
TOENNIES, JP .
JOURNAL OF CHEMICAL PHYSICS, 1981, 74 (02) :1017-1025
[8]   Comparing the dynamical effects of symmetric and antisymmetric stretch excitation of methane in the Cl+CH4 reaction [J].
Bechtel, HA ;
Camden, JP ;
Brown, DJA ;
Zare, RN .
JOURNAL OF CHEMICAL PHYSICS, 2004, 120 (11) :5096-5103
[9]   A refined H-3 potential energy surface [J].
Boothroyd, AI ;
Keogh, WJ ;
Martin, PG ;
Peterson, MR .
JOURNAL OF CHEMICAL PHYSICS, 1996, 104 (18) :7139-7152
[10]   Ab initio calculations of coupled potential energy surfaces for the Cl(2P3/2,2P1/2)+H2 reaction [J].
Capecehi, G ;
Werner, HJ .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2004, 6 (21) :4975-4983