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离子捕获双原子分子过程中λ-双重态之间的非绝热跃迁。

Nonadiabatic transitions between lambda-doubling states in the capture of a diatomic molecule by an ion.

作者信息

Auzinsh M, Dashevskaya E I, Litvin I, Nikitin E E, Troe J

机构信息

Department of Physics, University of Latvia, Riga, Latvia.

出版信息

J Chem Phys. 2008 May 14;128(18):184304. doi: 10.1063/1.2913519.

Abstract

The low-energy capture of a dipolar diatomic molecule in an adiabatically isolated electronic state with a good quantum number Omega (Hund's coupling case a) by an ion occurs adiabatically with respect to rotational transitions of the diatom. However, the capture dynamics may be nonadiabatic with respect to transitions between the pair of the Lambda-doubling states belonging to the same value of the intrinsic angular momentum j. In this work, nonadiabatic transition probabilities are calculated which define the Lambda-doubling j-specific capture rate coefficients. It is shown that the transition from linear to quadratic Stark effect in the ion-dipole interaction, which damps the T(-1/2) divergence of the capture rate coefficient calculated with vanishing Lambda-doubling splitting, occurs in the adiabatic regime with respect to transitions between Lambda-doubling adiabatic channel potentials. This allows one to suggest simple analytical expressions for the rate coefficients in the temperature range which covers the region between the sudden and the adiabatic limits with respect to the Lambda-doubling states.

摘要

在具有良好量子数Ω(洪德耦合情况a)的绝热孤立电子态中的双极双原子分子,被离子低能俘获时,相对于双原子分子的转动跃迁是绝热发生的。然而,对于属于相同内禀角动量j值的一对Λ-双重态之间的跃迁,俘获动力学可能是非绝热的。在这项工作中,计算了非绝热跃迁概率,这些概率定义了特定于Λ-双重态j的俘获速率系数。结果表明,离子 - 偶极相互作用中从线性斯塔克效应到二次斯塔克效应的转变,抑制了在Λ-双重分裂消失时计算的俘获速率系数的T(-1/2)发散,这一转变在相对于Λ-双重绝热通道势之间的跃迁的绝热区域中发生。这使得人们能够针对温度范围提出速率系数的简单解析表达式,该温度范围涵盖了相对于Λ-双重态从突然极限到绝热极限之间的区域。

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