物理化学学报 >> 1990, Vol. 6 >> Issue (01): 23-31.doi: 10.3866/PKU.WHXB19900105

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I2分子B(ν′=43)能级在超音速射流中振动弛豫速率的定量测量

马之骝;黄瑞平   

  1. 中国科学院大连化学物理研究所
  • 收稿日期:1988-06-06 修回日期:1989-01-16 发布日期:1990-02-15
  • 通讯作者: 马之骝

Quantitative Measurements of Vibrational Relaxation Rates in Supersonic Jets of I2 B(ν′=43) State

Ma Zhi-Liu;Huang Rui-Ping   

  1. Dalian Institute of Chemical Physics Academia Sinica
  • Received:1988-06-06 Revised:1989-01-16 Published:1990-02-15
  • Contact: Ma Zhi-Liu

摘要: 利用改变观察场位置的方法, 用LIF法定量测量了超音速射流中I_2B(υ’=43)能极的振动弛豫速率. 首次获得了Ar, N_2和CO等分子的驰豫截面. 结果表明, 低温射流中振动弛豫速率呈负温度关系, 对载气He和H_2, 主要弛豫过程是△υ=-1通道, 但对Ar, N_2和CO等载气, 多振动量子传输很显著, 特别是对双原子分子, 最可几弛豫通道不再是△υ=-1过程. 这违反了能隙定律.这种现象可用亚稳态络合物的形成来解释。

Abstract: A LIF technique that employs a varying view field has been developed to give quantitative measurement for the vibrational relaxation rates of I_2 B(v′=43) state in supersonic jets. The data for Ar, N_2 and CO are obtained for the first time. The results have shown that the measured vibrational relaxation rates in cold jets bear an inverse tempeature dependence. For He and H_2 carrier gases, the dominant relaxation process is the usual △v=-1 process. For Ar, N_2 and CO, however, the most probable relaxation pathway is no longer Δv=-1 process, which apparently violates the energy gap law. These observations are adequately explained by a metastable complex formation mechanism.