Haverd V E, Lewis B R, Gibson S T, Stark G
Research School of Physical Sciences and Engineering, The Australian National University, Canberra, Australian Capital Territory 0200, Australia.
J Chem Phys. 2005 Dec 1;123(21):214304. doi: 10.1063/1.2134704.
A coupled-channel Schrodinger equation (CSE) model of N2 photodissociation, which includes the effects of all interactions between the b, c, and o 1Pi u and the C and C' 3Pi u states, is employed to study the effects of rotation on the lowest-upsilon 1Pi u-X 1Sigmag+(upsilon,0) band oscillator strengths and 1Pi u predissociation linewidths. Significant rotational dependences are found which are in excellent agreement with recent experimental results, where comparisons are possible. New extreme-ultraviolet (EUV) photoabsorption spectra of the key b 1Pi u<--X 1Sigmag +(3,0) transition of N2 are also presented and analyzed, revealing a b(upsilon=3) predissociation linewidth peaking near J=11. This behavior can be reproduced only if the triplet structure of the C state is included explicitly in the CSE-model calculations, with a spin-orbit constant A approximately 15 cm(-1) for the diffuse C(upsilon=9) level which accidentally predissociates b(upsilon=3). The complex rotational behavior of the b-X(3,0) and other bands may be an important component in the modeling of EUV transmission through nitrogen-rich planetary atmospheres.
采用一个N₂光解离的耦合通道薛定谔方程(CSE)模型,该模型包含b、c和o ¹Πu与C和C' ³Πu态之间所有相互作用的影响,来研究转动对最低υ ¹Πu - X ¹Σg⁺(υ,0)带振子强度和¹Πu预解离线宽的影响。发现了显著的转动依赖性,在可进行比较的情况下,与最近的实验结果非常吻合。还给出并分析了N₂关键的b ¹Πu ← X ¹Σg⁺(3,0)跃迁的新的极紫外(EUV)光吸收光谱,揭示了b(υ = 3)预解离线宽在J = 11附近达到峰值。只有在CSE模型计算中明确包含C态的三重态结构,对于意外预解离b(υ = 3)的漫射C(υ = 9)能级,自旋 - 轨道常数A约为15 cm⁻¹时,才能重现这种行为。b - X(3,0)和其他带的复杂转动行为可能是模拟通过富含氮的行星大气的EUV传输的一个重要组成部分。