The radiative characteristics of the rovibronic states of the hydrogen molecule:: IV.: Relative probabilities of the r3IIg-, s3Δg-→c3IIu± spontaneous transitions of the H2 molecule

被引:5
作者
Astashkevich, S. A. [1 ]
Lavrov, B. P. [1 ]
Modin, A. V. [1 ]
Umrikhin, I. S. [1 ]
机构
[1] St Petersburg State Univ, St Petersburg 199164, Russia
关键词
D O I
10.1007/s11826-008-1004-4
中图分类号
O64 [物理化学(理论化学)、化学物理学]; O56 [分子物理学、原子物理学];
学科分类号
070203 ; 070304 ; 081704 ; 1406 ;
摘要
A statistical analysis of the available literature data and data obtained in this work on the wave numbers of the lines that appear in triplet-triplet rovibronic transitions of the H-2 molecule was performed. This allowed us to verify and refine the controversial identification of spectral lines and find the optimum rovibronic level energy values for the c(3)II(u)(+/-), r(3)II(g)(-), and s(3)Delta(-)(g) states. The ratios between the line strengths of the P, Q, and R branches of the (4d pi)r3 Pi g-, (4d delta)s(3)Delta(-)(g)-> (2p pi)c(3)Pi(+/-)(u) band systems of the H-2 molecule were measured systematically. The calculation results obtained in the Frank-Condon approximation differed substantially (by up to two orders of magnitude) from the experimental data. The dependences of the ratios between rovibronic line strengths of the r(3)Pi(-)(g)-> c(3)Pi(+/-)(u) and s(3)Delta(-)(g) -> c(3)Pi(+/-)(u) transitions on the rotational quantum number N' of the upper level were found to correlate with each other. The deviations of adiabatic theory increase as N' grows, which is evidence of an important role played by electronic-rotational interactions in the perturbation of transition probabilities. The experimental ratios between the probabilities of rovibronic transitions satisfactorily agree with the results of calculations within the framework of the simple nonadiabatic model taking into account electronic-rotational interaction of radiating adiabatic states in the approximation of pure precession. The dependences of transition probabilities on N' were obtained for the first time for the first four diagonal bands of the r(3)Pi(-)(g), s(3)Delta(-)(g)-> c(3)Pi(+/-)(u) transitions.
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页码:16 / 31
页数:16
相关论文
共 31 条
[1]   Fluorescence lifetimes of the P1Σg+, R1Πg, and S1Δg states of D2 [J].
Aita, H ;
Yoshinari, T ;
Ogi, Y ;
Tsukiyama, K .
JOURNAL OF MOLECULAR SPECTROSCOPY, 2005, 234 (01) :99-105
[2]   Fluorescence lifetimes of the O1Σg+, P1Σg+, R1Πg, and S1Δg states of H2 [J].
Aita, H ;
Ogi, Y ;
Tsukiyama, K .
JOURNAL OF MOLECULAR SPECTROSCOPY, 2005, 232 (02) :315-322
[3]  
[Anonymous], 1969, ROTATIONAL STRUCTURE
[4]   The radiative characteristics of hydrogen rovibronic states:: II.: The probabilities of the i3Πg-, j3Δg- → b3Σu+, c3Πu± spontaneous transitions in H2, HD, and D2 [J].
Astashkevich, S. A. ;
Lavrov, B. P. .
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B, 2007, 1 (01) :1-14
[5]   Observation of Perturbations in the rovibronic transition probabilities for the (4d)r3II-g, (4d) s3Δ-g → (2p)c3II±u band Systems of the H2 molecule [J].
Astashkevich, S. A. ;
Lavrov, B. P. ;
Modin, A. V. ;
Umrikhin, I. S. .
OPTICS AND SPECTROSCOPY, 2007, 102 (03) :363-366
[6]   Semiempirical investigation of perturbations of the g factors of electronic-vibrational-rotational levels of hydrogen:: III.: The r3Π-g s3Δg- states of the H2 and D2 molecules [J].
Astashkevich, S. A. .
OPTICS AND SPECTROSCOPY, 2006, 101 (04) :508-515
[7]  
Astashkevich S. A., 1994, Optics and Spectroscopy, V76, P38
[8]  
Astashkevich S. A., 2006, KHIM FIZ, V25, P3
[9]  
ASTASHKEVICH SA, 1994, OPT SPEKTROSK+, V76, P33
[10]   Radiative characteristics of 3p Sigma,Pi; 3d Pi(-),Delta(-) states of H-2 and determination of gas temperature of low pressure hydrogen containing plasmas [J].
Astashkevich, SA ;
Kaning, M ;
Kaning, E ;
Kokina, NV ;
Lavrov, BP ;
Ohl, A ;
Ropcke, J .
JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER, 1996, 56 (05) :725-751