Abstract：Collisional deactivation rate constants, k5(M) for HBr(Χ1Σ+ ν″=5) by M= H2, N2, CO2, and HBr were obtained using the degenerated stimulated hyper-Raman (OSHR) pumping method in a pumping-probe configuration. High- resolution transient laser induced fluorescence (LIF) was used to detect collisionally relaxed HBr. For M=CO2, an efficient near-resonant 1-1 vibration-to- vibration (V-V) energy exchange was observed. It appeared that the presence of a strong infrared-active vibrational mode was a favorable situation for an efficient V-V energy transfer. A 1-1 resonance exciting the infrared forbidden N2(1←0) vibration was also observed, but it was 2 orders of magnitude smaller than that of CO2. Self-relaxation rate constants of HBr (ν″=5) were measured. Single quantum relaxation accounted for about 70% of the total relaxation out of state ν″=5, and two-quantum relaxation made contributions (25%) to the vibrational relaxation at this vibrational energy. Direct evidence for 2-1 resonance in HBr (ν″=5)+H2 was observed. Initial preparation of HBr (ν″=5) resulted in nearly no population in HBr (ν″=4), but direct population of HBr (ν″=3). Therefore only 2-1 resonant energy transfer was important for H2 relaxation. The state specific rate constant for HBr was obtained by the analysis of the state-to-state relaxation data. It was found that the data could be fitted with one adjustable normaligation parameter using a single-quantum relaxation model, which restricted the rate constant. A strong mass effect on the vibrational relaxation rate constant was observed. A further check of the character of the V-V resonant energy transfer in highly vibrationally excited HBr was the temperature dependence of the rate constants. For M=CO2, the temperature dependence of the 1-1 near-resonant energy transfer rate constats was found to be inverted. In contranst, the temperature dependence of the relaxation rate constants for M= H2 and HBr was normal. For M=N2, a weak but position temperature dependence was found. It suggested that this resonance occurred by a different mechanism compared with that in CO2.
刘 静，戴 康，沈异凡. HBr(X1Σ+ ν″=5)分子与H2, N2, CO2和HBr间的近共振振动-振动能量转移[J]. 光谱学与光谱分析, 2017, 37(10): 3000-3005.
LIU Jing, DAI Kang, SHEN Yi-fan. Resonent Vibration-Vibration Energy Transfer Between Vibrationally Excited HBr (Χ1Σ+ ν″=5) and H2, N2, CO2, and HBr. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(10): 3000-3005.
[1] Strekalov M L. Chem. Phys. Lett., 2006, 431(11): 1.
[2] Havey D K, Liu Q, Li Z. J. Phys. Chem. A, 2007, 111(51): 13321.
[3] Watanabe S S, Fujii H, Kohguchi H, et al. J. Phys. Chem. A, 2008, 112: 9290.
[4] Liu C L, Hsu C H, Hsu Y C, et al. J. Chem. Phys.，2008, 128: 124320.
[5] Hsu C H, Liu C L, Hsu Y C, et al. J. Chem. Phys.，2008, 129: 044301.
[6] Havey D K, Du J, Liu Q N, et al. J. Phys. Chem. A, 2010, 114: 1569.
[7] Du J, Sassin N A, Havey D K, et al. J. Phys. Chem. A, 2013, 117: 12104.
[8] Yamasaki K, Fujii H, Watanabe S, et al. Phys. Chem. Chem. Phys., 2006, 8: 1936.
[9] Wang S Y, Zhang B, Zhu D H, et al. Spectrochim. Acta A, 2012, 96: 517.
[10] Liu J, Shen Y F, and Dai K. Chem. Phys., 2013, 425(11): 62.
[11] Fedorov D A, Derevianko A, Varganov S A. J. Chem. Phys., 2014, 140: 184315.
[12] Jongma R T, and Wodtke A M. J. Chem. Phys., 1999, 111: 10957.
[13] Lawrence W G, Marter T A V, Nowlin M L, et al. J. Chem. Phys., 1997, 106: 127.
[14] Frerichs H, Lenzer T, Luther K. Phys. Chem. Chem. Phys.，2005, 7(4): 620.
[15] Alghazi A, Liu J, Dai K, et al. Chem. Phys., 2015, 448: 76.
[16] Mu B X, Cui X H, Shen Y F, et al. Spectrochim. Acta A, 2015, 148: 299.
[17] Kabir M H, Antonov I O, Heaven M C. J. Chem. Phys., 2009, 130: 074305.
[18] Kabir M H, Antonov I O, Merritt J M, et al. J. Phys. Chem. A, 2010, 114: 11109.
[19] Yang X M, Kim E H, Wodtke A M. J. Chem. Phys.，1992, 96: 5111.
[20] Flynn G W, Parmenter C S, Wodtke A M. J. Phys. Chem., 1996, 100(31): 12817.
[21] Mack J A, Mikulecky K, and Wodtke A M. J. Chem. Phys., 1996, 105: 4105.
