The vibrational dependence of dissociative recombination: Rate constants for N2+

被引:4
|
作者
Guberman, Steven L. [1 ]
机构
[1] Inst Sci Res, Winchester, MA 01890 USA
来源
JOURNAL OF CHEMICAL PHYSICS | 2014年 / 141卷 / 20期
基金
美国国家科学基金会;
关键词
ELECTRON-ION RECOMBINATION; GAUSSIAN-BASIS SETS; TEMPERATURE-DEPENDENCE; RYDBERG STATES; MOLECULAR-IONS; COEFFICIENTS; ABSORPTION; EXCITATION; CL;
D O I
10.1063/1.4901892
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
Dissociative recombination rate constants are reported with electron temperature dependent uncertainties for the lowest 5 vibrational levels of the N-2(+) ground state. The rate constants are determined from ab initio calculations of potential curves, electronic widths, quantum defects, and cross sections. At 100 K electron temperature, the rate constants overlap with the exception of the third vibrational level. At and above 300 K, the rate constants for excited vibrational levels are significantly smaller than that for the ground level. It is shown that any experimentally determined total rate constant at 300 K electron temperature that is smaller than 2.0 x 10(-7) cm(3)/s is likely to be for ions that have a substantially excited vibrational population. Using the vibrational level specific rate constants, the total rate constant is in very good agreement with that for an excited vibrational distribution found in a storage ring experiment. It is also shown that a prior analysis of a laser induced fluorescence experiment is quantitatively flawed due to the need to account for reactions with unknown rate constants. Two prior calculations of the dissociative recombination rate constant are shown to be inconsistent with the cross sections upon which they are based. The rate constants calculated here contribute to the resolution of a 30 year old disagreement between modeled and observed N-2(+) ionospheric densities. (C) 2014 AIP Publishing LLC.
引用
收藏
页数:12
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