Vector Correlation Analysis for Inelastic and Reactive Collisions between Partners Possessing Spin and Orbital Angular Momentum

被引:23
作者
Balint-Kurti, Gabriel G. [1 ]
Vasyutinskii, Oleg S. [2 ]
机构
[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
[2] Russian Acad Sci, Ioffe Physicotech Inst, St Petersburg 194021, Russia
关键词
CHEMICAL-REACTIONS; ROTATIONAL ALIGNMENT; MOLECULAR-DYNAMICS; POLARIZATION; SCATTERING; STEREODYNAMICS; SYMMETRY; ATOMS; ORIENTATION; DEPENDENCE;
D O I
10.1021/jp902796v
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
A general reactive collision of the type A + B -> C + D is considered where both the collision partners (A and B) or the products (C and D) may possess internal, i.e., spin, orbital or rotational, angular momenta. Compact expressions are derived using a rigorous quantum mechanical analysis for the angular momentum anisotropy of either of the products (C or D) arising from an initially polarized distribution of the reactant angular momentum. The angular momentum distribution of the product is expressed in terms of canonical spherical tensors multiplied by anisotropy-transforming coefficients c(Kiqk)(K)(K-r,L). These coefficients act as transformation coefficients between the angular momentum anisotropy of the reactants and that of the product. They are independent of scattering angle but depend on the details of the scattering dynamics. The relationship between the coefficients c(Kiqk)(K)(K-r,L) and the body-fixed scattering S matrix is given and the methodology for the quantum mechanical calculation of the anisotropy-transforming coefficients is clearly laid out. The anisotropy-transforming coefficients are amenable to direct experimental measurement in a similar manner to vector correlation and alignment parameters in photodissociation processes. A key aspect of the theory is the use of projections of both reactant and product angular momenta onto the product recoil vector direction. An important new conservation rule is revealed through the analysis, namely that if the state multipole for reactant angular momentum distribution has a projection q(k) onto the product recoil vector the state multipoles for the product angular momentum distribution all have this same projection. Expressions are also presented for the distribution of the product angular momentum when its components are evaluated relative to the space-fixed Z-axis. Notes with detailed derivations of all the formulas are available as Supporting Information.
引用
收藏
页码:14281 / 14290
页数:10
相关论文
共 55 条
  • [1] Analysis of the H+D2 reaction mechanism through consideration of the intrinsic reactant polarisation
    Aldegunde, J.
    Alvarino, J. M.
    Kendrick, B. K.
    Rabanos, V. Saez
    de Miranda, M. P.
    Aoiz, F. J.
    [J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2006, 8 (42) : 4881 - 4896
  • [2] How reactants polarization can be used to change and unravel chemical reactivity
    Aldegunde, J
    de Miranda, MP
    Haigh, JM
    Kendrick, BK
    Sáez-Rábanos, V
    Aoiz, FJ
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (28) : 6200 - 6217
  • [3] Quantum mechanical limits to the control of atom-diatom chemical reactions through the polarisation of the reactants
    Aldegunde, Jesus
    Aoiz, F. Javier
    de Miranda, Marcelo P.
    [J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (08) : 1139 - 1150
  • [4] M-DEPENDENCE IN ROTATIONALLY INELASTIC-COLLISIONS IN CELL EXPERIMENTS - IMPLICATIONS OF AN IRREDUCIBLE TENSOR EXPANSION FOR MOLECULES IN 1-SIGMA ELECTRONIC STATES
    ALEXANDER, MH
    DAVIS, SL
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1983, 78 (11) : 6754 - 6762
  • [5] [Anonymous], 1969, Quantum Mechanics of Molecular Rate Processes
  • [6] AOIZ J, 1993, J CHEM SOC FARADAY T, V89, P1427
  • [7] COORDINATES FOR MOLECULAR-DYNAMICS - ORTHOGONAL LOCAL SYSTEMS
    AQUILANTI, V
    CAVALLI, S
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1986, 85 (03) : 1355 - 1361
  • [8] STEREODIRECTED STATES IN MOLECULAR-DYNAMICS - A DISCRETE BASIS REPRESENTATION FOR THE QUANTUM-MECHANICAL SCATTERING MATRIX
    AQUILANTI, V
    CAVALLI, S
    GROSSI, G
    ANDERSON, RW
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (21) : 8184 - 8193
  • [9] Blum K., 1981, Density Matrix Theory and Applications
  • [10] Product state resolved dynamics of elementary reactions
    Brouard, M
    O'Keeffe, P
    Vallance, C
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (15) : 3629 - 3641