Axially nonadiabatic channel treatment of low-energy capture in ion-rotating diatom collisions

被引:10
作者
Dashevskaya, EI
Litvin, I
Nikitin, EE
Oref, I
Troe, J [1 ]
机构
[1] Technion Israel Inst Technol, Dept Chem, IL-32000 Haifa, Israel
[2] Univ Gottingen, Inst Chem Phys, D-37077 Gottingen, Germany
关键词
D O I
10.1021/jp040084o
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
The quantum version of an axially nonadiabatic channel (ANC) approximation, introduced in an earlier article for the calculation of complex-formation cross sections and rate constants in ion-diatom collisions [Maergoiz, A. I.; Nikitin, E. E.; Troe, J.; Ushakov, V. G. J. Chem. Phys. 2002, 117, 4201-4213] is tested against accurate quantum results. Cross sections and rate constants are determined for several representative systems with the participation of a diatom in the state j = 1, assuming various long-range potentials between the collision partners, such as anisotropic ion-induced dipole, second-order charge-permanent dipole, and first-order charge-quadrupole interaction. The ANC approximation well reproduces accurate quantum results in the perturbed rotor limit, while the standard quantum adiabatic channel (AC) approximation fails at low energy due to neglect of Coriolis coupling. However, the low-energy extrapolation of classical adiabatic channel results (ACCI) provides a reasonable approximation both to accurate and quantal ANC results down to collision energies when only few partial cross sections determine the total capture cross section. This unexpected feature of the ACCI approximation is due to two effects: (a) an artificial simulation of tunneling transmission and overbarrier reflection at centrifugal barriers by introducing a continuous distribution over total angular momenta and (b) a slight effective lowering of the centrifugal barriers compared to centrifugal barriers within the AC model. Low-temperature quantum rate constants are also presented.
引用
收藏
页码:8703 / 8712
页数:10
相关论文
共 29 条
[2]   DYNAMIC ORIENTATION OF DIATOMIC FRAGMENTS FORMED IN THE DECOMPOSITION OF STATISTICAL TRIATOMIC COMPLEXES .2. CLASSICAL SIMULATION [J].
BERENGOLTS, A ;
DASHEVSKAYA, EI ;
NIKITIN, EE ;
TROE, J .
CHEMICAL PHYSICS, 1995, 195 (1-3) :283-289
[4]   Reflection above potential steps [J].
Cote, R ;
Friedrich, H ;
Trost, J .
PHYSICAL REVIEW A, 1997, 56 (03) :1781-1787
[5]   LONG-RANGE, NONADIABATIC EFFECTS IN STATISTICAL ADIABATIC CHANNEL MODELS - DYNAMIC ORIENTATION OF DIATOMIC FRAGMENTS FORMED IN THE DECOMPOSITION OF LONG-LIVED TRIATOMIC COMPLEXES [J].
DASHEVSKAYA, EI ;
NIKITIN, EE ;
TROE, J .
JOURNAL OF CHEMICAL PHYSICS, 1990, 93 (11) :7803-7807
[6]   Low-temperature behavior of capture rate constants for inverse power potentials [J].
Dashevskaya, EI ;
Maergoiz, AI ;
Troe, J ;
Litvin, I ;
Nikitin, EE .
JOURNAL OF CHEMICAL PHYSICS, 2003, 118 (16) :7313-7320
[7]  
DASHEVSKAYA EI, IN PRESS J CHEM PHYS
[8]   RATE-CONSTANT CALCULATIONS ON THE C+ +HCL REACTION [J].
DATEO, CE ;
CLARY, DC .
JOURNAL OF CHEMICAL PHYSICS, 1989, 90 (12) :7216-7228
[9]  
DUBERNET ML, 1989, PHYSICA D, V13, P255
[10]   Near-threshold quantization and scattering for deep potentials with attractive tails [J].
Eltschka, C ;
Moritz, MJ ;
Friedrich, H .
JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 2000, 33 (19) :4033-4051