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通过发射光谱和理论对keV N2(+*)/He与N2(+*)/Ar碰撞的比较

Comparison of keV N2(+*)/He and N2(+*)/Ar collisions by emission spectroscopy and theory.

作者信息

Poon Clement, Lin Yawei, Mayer Paul M

机构信息

Department of Chemistry, University of Ottawa, 10 Marie-Curie, Ottawa, Ontario, Canada K1N 6N5.

出版信息

J Phys Chem A. 2008 Aug 28;112(34):7761-7. doi: 10.1021/jp8017524. Epub 2008 Aug 5.

Abstract

Collision-induced emission spectra from 190-1020 nm were obtained for N 2 (+)/Ar collisions at laboratory frame collision energies from 2 to 8 keV. The relative emission intensities of N 2 (+), N (+), and N () are independent of the ion translational energy within the studied energy range, supporting the curve-crossing mechanism for collisional excitation. The role of the target gas in keV N 2 (+)/He and N 2 (+)/Ar collisions was investigated by both emission spectroscopy and theoretical calculations. Adiabatic potential energy surfaces calculated at the CISD/6-311+G(2df) level of theory for N 2 (+)/He and N 2 (+)/Ar collisions indicate that excitation to the A (2)Pi u and B (2)Sigma u (+) states involves curve-crossing first to the C (2)Sigma u (+) state, and the difference in N 2 (+) emission intensities from the two systems can be accounted for by the slope difference at the crossing points based on the Landau-Zener curve-crossing model.

摘要

在实验室坐标系碰撞能量为2至8 keV的条件下,获得了190 - 1020 nm范围内N₂(+) / Ar碰撞的碰撞诱导发射光谱。在研究的能量范围内,N₂(+)、N(+)和N()的相对发射强度与离子平移能量无关,这支持了碰撞激发的曲线交叉机制。通过发射光谱和理论计算研究了keV能量下N₂(+) / He和N₂(+) / Ar碰撞中靶气体的作用。在CISD / 6 - 311 + G(2df)理论水平下计算的N₂(+) / He和N₂(+) / Ar碰撞的绝热势能面表明,激发到A(²)Πᵤ和B(²)Σᵤ⁺态首先涉及到曲线交叉到C(²)Σᵤ⁺态,基于朗道 - 齐纳曲线交叉模型,两个体系中N₂(+)发射强度的差异可以由交叉点处的斜率差异来解释。

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