Three Reaction Pathways in the H plus HCO → H2 + CO Reaction

被引:44
作者
Christoffel, Kurt M. [2 ]
Bowman, Joel M. [1 ]
机构
[1] Emory Univ, Dept Chem, Atlanta, GA 30322 USA
[2] Augustana Coll, Dept Chem, Rock Isl, IL 61201 USA
关键词
POTENTIAL-ENERGY SURFACE; CORRELATED MOLECULAR CALCULATIONS; ABSTRACTION REACTION DYNAMICS; GAUSSIAN-BASIS SETS; ROAMING MECHANISM; TRANSITION-STATE; DISSOCIATION; PHOTODISSOCIATION; FORMALDEHYDE; ATOMS;
D O I
10.1021/jp810517e
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 report quasiclassical trajectory calculations of the H + HCO -> H-2 + CO reaction using a recent global potential energy surface. Three microscopic pathways are identified for this reaction. One is a direct abstraction, and the others both proceed via initial formation of a long-lived complex in the H,CO well followed by reaction (a) over the molecular saddle point transition state or (b) via a roaming pathway previously identified for the unimolecular photodissociation reaction [Townsend et al., Science 2004, 306, 1158]. Cross sections and product internal energy distributions for each pathway are calculated for five initial collision energies.
引用
收藏
页码:4138 / 4144
页数:7
相关论文
共 32 条
[21]   Quasiclassical trajectory calculations of acetaldehyde dissociation on a global potential energy surface indicate significant non-transition state dynamics [J].
Shepler, Benjamin C. ;
Braams, Bastiaan J. ;
Bowman, Joel M. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (34) :8282-8285
[22]   Near threshold dynamics and dissociation energy of the reaction H2CO->HCO+H [J].
Terentis, AC ;
Kable, SH .
CHEMICAL PHYSICS LETTERS, 1996, 258 (5-6) :626-632
[23]   The roaming atom: Straying from the reaction path in formaldehyde decomposition [J].
Townsend, D ;
Lahankar, SA ;
Lee, SK ;
Chambreau, SD ;
Suits, AG ;
Zhang, X ;
Rheinecker, J ;
Harding, LB ;
Bowman, JM .
SCIENCE, 2004, 306 (5699) :1158-1161
[24]   Classical trajectory study of the reaction between H and HCO [J].
Troe, Juergen ;
Ushakov, Vladimir .
JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (29) :6610-6614
[25]   AN EFFICIENT INTERNALLY CONTRACTED MULTICONFIGURATION REFERENCE CONFIGURATION-INTERACTION METHOD [J].
WERNER, HJ ;
KNOWLES, PJ .
JOURNAL OF CHEMICAL PHYSICS, 1988, 89 (09) :5803-5814
[26]  
WERNER HJ, MOLPRO PACKAGE AB IN
[27]  
Wilson E.Bright., 1980, MOL VIBRATIONS
[28]   GAUSSIAN-BASIS SETS FOR USE IN CORRELATED MOLECULAR CALCULATIONS .3. THE ATOMS ALUMINUM THROUGH ARGON [J].
WOON, DE ;
DUNNING, TH .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (02) :1358-1371
[29]   Quasiclassical trajectory study of the reaction of fast H atoms with C-H stretch excited CHD3 [J].
Xie, Zhen ;
Bowman, Joel M. .
CHEMICAL PHYSICS LETTERS, 2006, 429 (4-6) :355-359
[30]   Signatures of H2CO photodissociation from two electronic states [J].
Yin, HM ;
Kable, SH ;
Zhang, X ;
Bowman, JM .
SCIENCE, 2006, 311 (5766) :1443-1446