Collisional depolarization of NO(A) by He and Ar studied by quantum beat spectroscopy

被引:29
作者
Brouard, M. [1 ]
Chadwick, H. [1 ]
Chang, Y. -P. [1 ]
Cireasa, R. [1 ]
Eyles, C. J. [1 ]
La Via, A. O. [1 ]
Screen, N. [1 ]
Aoiz, F. J. [2 ]
Klos, J. [3 ]
机构
[1] Univ Oxford, Dept Chem, Phys & Theoret Chem Lab, Oxford OX1 3QZ, England
[2] Univ Complutense, Fac Quim, Dept Quim Fis, E-28040 Madrid, Spain
[3] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA
基金
美国国家科学基金会; 英国工程与自然科学研究理事会;
关键词
LASER-INDUCED FLUORESCENCE; ROTATIONAL ENERGY-TRANSFER; POLARIZATION SPECTROSCOPY; INELASTIC-COLLISIONS; VECTOR CORRELATION; CHEMICAL-REACTIONS; STATE; NO; ALIGNMENT; OH;
D O I
10.1063/1.3212608
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
Zeeman and hyperfine quantum beat spectroscopies have been used to measure the total elastic plus inelastic angular momentum depolarization rate constants at 300 K for NO(A (2)Sigma(+)) in the presence of He and Ar. In the case of Zeeman quantum beats it is shown how the applied magnetic field can be used to allow measurement of depolarization rates for both angular momentum orientation and alignment. For the systems studied here, collisional loss of alignment is more efficient than loss of orientation. In the case of NO(A) with He, and to a lesser extent NO(A) with Ar, collisional depolarization is found to be a relatively minor process compared to rotational energy transfer, reflecting the very weak long-range forces in these systems. Detailed comparisons are made with quantum mechanical and quasiclassical trajectory calculations performed on recently developed potential energy surfaces. For both systems, the agreement between the calculated depolarization cross sections and the present measurements is found to be very good, suggesting that it is reasonable to consider the NO(A) bond as frozen during these angular momentum transferring collisions. A combination of kinematic effects and differences in the potential energy surfaces are shown to be responsible for the differences observed in depolarization cross section with He and Ar as a collider. (C) 2009 American Institute of Physics. [doi:10.1063/1.3212608]
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页数:15
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