Collisional intramultiplet relaxation of Cd(5s5p 3P0,1,2) by alkane hydrocarbons

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Abstract
Very rapid collisional intramultiplet relaxation of the intial distribution of Cd(3P0,1,2) quantum states produced in the process Cd(1P1)+ RH → Cd(3P0,1,2) + RH, where RH are the alkane hydrocarbons, has been observed. This relaxation has been characterized by pulsed laser excitation of Cd(1P1) and determination of Cd(3P2,1,0) relative populations at short time delays using laser‐induced fluorescence. The population of the Cd(3P1) state was also monitored by time‐resolved fluorescence at 3261 Å. It was shown that not only are the cross sections for collisional conversion of Cd(3P2) to Cd(3P1) or Cd(3P0) quite large, but that the Cd(3PJ) states are produced with substantial amounts of translation energy in the Cd (1P1)‐alkane deactivation process, thus increasing the effective Cd (3P0,1,2) collision frequency at short times. Using kinetic simulation techniques, lower limits were estimated for the cross sections for intramultiplet relaxation of Cd (3P2) by several alkane hydrocarbons. Analysis of Cd(3P1) fluorescence data at longer delay times, where translational equilibrium had been established, allowed the determination of cross sections for intramultiplet relaxation of Cd(3P1) to Cd(3P0) by the alkanes studied. The magnitudes of the cross sections are discussed within the framework of the Baylis–Krause theory of electronic‐to‐rotational energy transfer originally developed to explain the intramultiplet relaxation of Cs(2P3/2) by the isotopic methanes.

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