Prediction of reduced falloff curves for recombination reactions at low temperatures

被引：30

作者：

Cobos, CJ ^{[1
]}

Troe, J

机构：

[1] Univ Nacl De La Plata, INIFTA, Fac Ciencias Exactas, La Plata, Argentina

[2] Univ Gottingen, Inst Chem Phys, D-37077 Gottingen, Germany

来源：

ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS | 2003年 / 217卷 / 08期

关键词：

recombination reactions; falloff curves; reaction kinetics; atmospheric chemistry;

D O I：

10.1524/zpch.217.8.1031.20428

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：

Strong collision falloff curves for barrierless recombination reactions at low temperatures are calculated taking into account transitional modes only. Specific rate constants k(E, J) from statistical adiabatic channel/classical trajectory (SACM/CT) calculations are used. Broadening factors of the falloff curves are found to depend only weakly on the temperature. A systematic analysis of the influence of the centrifugal barriers E-0(J), which are governed by the potential energy surface of the bond energies E-0, and of the number of transitional modes is made. Guidelines for estimating center broadening factors and shape functions for the broadening factors are given.

引用

页码：1031 / 1044

页数：14

共 20 条

[1] Theoretical study of the OH+NO2 reaction:: formation of nitric acid and the hydroperoxyl radical [J].

Chakraborty, D ;

Park, J ;

Lin, MC .

CHEMICAL PHYSICS, 1998, 231 (01) :39-49

[2]

COBO CJ, IN PRESS

[3] Limiting high pressure rate coefficients for the Ho+No2→HONO2 reaction on ab initio potential energy surfaces [J].

Cobos, CJ .

REACTION KINETICS AND CATALYSIS LETTERS, 2003, 79 (02) :263-269

[4] THEORY OF THERMAL UNIMOLECULAR REACTIONS IN THE FALL-OFF RANGE .2. WEAK COLLISION RATE CONSTANTS [J].

GILBERT, RG ;

LUTHER, K ;

TROE, J .

BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1983, 87 (02) :169-177

[5] PARAMETRIZATION OF CHEMICALLY-ACTIVATED REACTIONS INVOLVING ISOMERIZATION [J].

KAZAKOV, A ;

WANG, H ;

FRENKLACH, M .

JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (41) :10598-10605

[6]

LUTHER K, 1979, 17TH S INT COMB PITT, P535

[7] Classical trajectory and statistical adiabatic channel study of the dynamics of capture and unimolecular bond fission.: VI.: Properties of transitional modes and specific rate constants k(E,J) [J].

Maergoiz, AI ;

Nikitin, EE ;

Troe, J ;

Ushakov, VG .

JOURNAL OF CHEMICAL PHYSICS, 2002, 117 (09) :4201-4213

[8] GENERAL EXPRESSION FOR UNIMOLECULAR RATE COEFFICIENTS IN THE FALLOFF REGION [J].

OREF, I .

JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (09) :3465-3469

[9] A GENERAL EXPRESSION FOR WEAK COLLISION UNIMOLECULAR RATE COEFFICIENTS IN THE FALLOFF REGION [J].

PAWLOWSKA, Z ;

OREF, I .

JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (02) :567-576

[10] INTERPOLATION FORMULAS FOR UNIMOLECULAR RATE COEFFICIENTS IN THE FALLOFF REGION [J].

PAWLOWSKA, Z ;

GARDINER, WC ;

OREF, I .

JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (19) :5024-5031

← 1 2 →