Dynamics of the reaction O(3P)+H2S→OH+SH.: 2.: State-resolved differential cross sections and angular momentum correlations

被引:12
作者
Costen, ML [1 ]
Hancock, G [1 ]
Ritchie, GAD [1 ]
机构
[1] Univ Oxford, Phys & Theoret Chem Lab, Oxford OX1 3QZ, England
关键词
D O I
10.1021/jp991990h
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
Measurements are reported of Doppler resolved polarized laser-induced fluorescence of the OH product of the O(P-3) + H2S reaction, leading to estimates of the differential cross sections and angular momentum correlations in the system. O(P-3) was produced with translational energy above the barrier to reaction by the polarized 355 nm photolysis of NO2. Three quantum states were studied in detail. For the most populated OH level, v" = 1, N" = 6, the scattering for the A" Lambda doublet was found to be largely sideways/backward, with the remaining energy appearing as product translation, and measurements of average Lambda doubler scattering showed similar behavior for the A' Lambda doubler. The same scattering dynamics were observed for the v" = 0, N" = 13 state. For the rotationless v" = 1, N" = 1 state the results were more ambiguous, but if the same distribution of available energy appeared in the SH fragment as deduced for the measurements on rotationally excited OH, then the scattering was seen to be clearly backward. Polarization measurements of the two OH levels with N" > 1 showed that the angular momentum vector J' was directed perpendicular to the plane containing the relative velocity vectors of reactants and products. A model of the scattering is proposed through a planar transition state and is able to account qualitatively for these observations of the vector characteristics of the reaction, together with the scalar attributes (quantum state populations) reported in the previous paper. The model predicts that the SH coproduct will be scattered largely forward with respect to the O(P-3) atom velocity, with low internal energy, and dominantly in the A" Lambda doubler.
引用
收藏
页码:10651 / 10663
页数:13
相关论文
共 47 条
[1]   VIBRATIONAL DISTRIBUTIONS AND RATE CONSTANTS FROM REACTIONS OF OXYGEN-ATOMS WITH HL, GEH4, SIH4, H2SE, AND H2S [J].
AGRAWALLA, BS ;
SETSER, DW .
JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (10) :5421-5432
[2]  
Alexander AJ, 1997, ISRAEL J CHEM, V37, P317
[3]   O(1D2)+H2→OH|v′≤4,N′⟩+H -: The anatomy of a reaction [J].
Alexander, AJ ;
Blunt, DA ;
Brouard, M ;
Simons, JP ;
Aoiz, FJ ;
Banares, L ;
Fujimura, Y ;
Tsubouchi, M .
FARADAY DISCUSSIONS, 1997, 108 :375-386
[4]   An experimental and quasiclassical study of the product state resolved stereodynamics of the reaction O(D-1(2))+H-2(v=0)->OH(X(2)Pi(3/2); v=0, N, f)+H [J].
Alexander, AJ ;
Aoiz, FJ ;
Brouard, M ;
Burak, I ;
Fujimura, Y ;
Short, J ;
Simons, JP .
CHEMICAL PHYSICS LETTERS, 1996, 262 (05) :589-597
[5]   Stereodynamics of the reaction O(D-1(2))+H-2(upsilon=0)->OH(X-2 Pi(i);upsilon'=0,N',f)+H: State-resolved linear and rotational angular momentum distributions [J].
Alexander, AJ ;
Aoiz, FJ ;
Banares, L ;
Brouard, M ;
Short, J ;
Simons, JP .
JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (41) :7544-7557
[6]   ANALYSIS OF PRODUCT DOPPLER-BROADENED PROFILES GENERATED FROM PHOTOINITIATED BIMOLECULAR REACTIONS [J].
AOIZ, FJ ;
BROUARD, M ;
ENRIQUEZ, PA ;
SAYOS, R .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1993, 89 (10) :1427-1434
[7]   Product rotational polarization in photon-initiated bimolecular reactions [J].
Aoiz, FJ ;
Brouard, M ;
Enriquez, PA .
JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (12) :4964-4982
[8]  
BALUCANI N, 1991, J CHEM PHYS, V94, P861
[9]   Unimolecular reaction dynamics of persistent collision complexes [J].
Brouard, M ;
Lambert, HM ;
Russell, CL ;
Short, J ;
Simons, JP .
FARADAY DISCUSSIONS, 1995, 102 :179-192
[10]   An experimental study of the dynamics of the reaction H+CO2→OH(v′,j′,f)+CO:: Product state-resolved differential cross sections and translational energy release distributions [J].
Brouard, M ;
Hughes, DW ;
Kalogerakis, KS ;
Simons, JP .
JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (47) :9559-9564