利用E-V传能模型研究亚稳态分子PCl(b^1∑^+)的猝灭过程

亚稳态分子猝灭机理的研究一直受到人们的极大重视。本文利用E-V传能模型对亚稳态分子PCl(b^1∑^+)的猝灭过程进行了定量处理。结果表明PCl(b^1∑^+)的猝灭是PCl(b^1∑^+→a^1Δ)跃迁和试剂分子端键X-Y振动能级近共振传能的结果, 与PCl(b^1∑^+→a^1Δ)跃迁的Franck-Condon因子及试剂分子端键X-Y振动的非谐性系数有关, 而且也受猝灭试剂分子极化率的影响。

Study on the quenching for PCl(b^1∑^+) by E-V model

Using the reaction of Ar(3P0, 2)+PCl3 as a source of PCl(b^1∑^+), we have measured the quenching rate constants of PCl (b, v'=0) for more than 20 quenchers. The E-V model is used to calculate the rate constants. Comparison of the calculated values with the experimental ones shows that the quenching of PCl(b) by the quencher molecules results from the electronic-to-vibrational energy resonant transfer and has relations to the Franck-Condon factors for the PCl(b, v'=0→a, v'=m) transition and the anharmonicities of the terminal bonds of the quencher molecules. In addition, the influence of the polarizability on the quenching rate constants is discussed.