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NH(X3Σ-)-He 体系精细结构分辨碰撞速率系数的计算。

Calculations of fine-structure resolved collisional rate coefficients for the NH(X3Σ-)-He system.

机构信息

Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland.

出版信息

J Chem Phys. 2011 Jan 14;134(2):024305. doi: 10.1063/1.3524311.

Abstract

We present fine-structure-resolved collisional rate coefficients for the NH(X(3)Σ(-))-He van der Waals complex. The calculations are based on the state-of-the-art potential energy surface [Cybulski et al., J. Chem. Phys. 122, 094307 (2005)]. Close-coupling calculations of the collisional excitation cross sections of the fine-structure levels of NH by He are calculated for total energies up to 3500 cm(-1), which yield, after thermal average, rate coefficients up to 350 K. The fine-structure splitting of rotational levels is taken into account rigorously. The propensity rules between fine-structure levels are reported, and it is found that F-conserving cross sections are much larger than F-changing cross sections, as expected from theoretical considerations. The calculated rate coefficients are compared with available experimental measurements at room temperature and a fairly good agreement is found between experimental and theoretical data. The agreement confirms the relatively good quality of the scattering calculations and also the accuracy of the potential energy surface used in this work. The new set of thermal rate coefficients for this system may be used for improvements in astrophysical and atmospherical modeling.

摘要

我们提出了 NH(X(3)Σ(-))-He 范德华复合物的精细结构分辨碰撞率系数。这些计算基于最先进的势能面[Cybulski 等人,J. Chem. Phys. 122, 094307 (2005)]。对于 NH 的精细结构能级与 He 的碰撞激发截面的紧密耦合计算,总能量高达 3500 cm(-1),经过热平均后,可得到高达 350 K 的速率系数。严格考虑了转动能级的精细结构分裂。报告了精细结构能级之间的倾向性规则,并且发现 F 守恒截面比 F 变化截面大得多,这与理论考虑相符。计算得到的速率系数与室温下的可用实验测量值进行了比较,在实验数据和理论数据之间发现了相当好的一致性。这种一致性证实了散射计算的相对高质量,也证实了本工作中使用的势能面的准确性。该系统的新的热速率系数集可用于改进天体物理和大气模拟。

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