Journal of Physical Chemistry A, Vol.103, No.20, 4016-4025, 1999
A pulsed source for Kr(5s[3/2](1)) resonance state atoms using two-photon-driven amplified spontaneous emission: Measurement of quenching rate constants
Krypton resonance state atoms, Kr(5s[3/2](1)), were generated in a static cell by two-photon laser excitation of the Kr(5p[5/2](2)) state with amplified spontaneous emission (ASE) at 877.7 and 810.4 nm in a few Torr of Kr gas. The 877.7 nm transition, which terminates on the resonance state, constitutes greater than or equal to 90% of the ASE intensity. The vacuum ultraviolet emission at 123.6 nm was used to monitor the Kr(5s[3/2](1)) concentration, which decayed with an effective lifetime of 2 mu s in the absence of added reagents. Total quenching rate constants at 300 K for the resonance state atoms were measured for 30 molecules by observing the decay rates of the Kr(5s[3/2](1)) atoms as a function of added reagent gas. The rate constants (cm(3) molecule(-1) s(-1)) range from 1.4 x 10(-11) for N-2 and 0.60 x 10(-11) for CF4 to (80-90) x 10(-11) for hydrocarbons. Rate constants for most polyatomic molecules exceed 30 x 10(-11) cm(3) molecule(-1) s(-1). Comparison to the quenching rate constants of the Kr(5s[3/2](2)) metastable atoms shows that the rate constants of the resonance states are similar to 35% larger for reagents with quenching cross sections larger than 20 Angstrom(2). For a set of 11 reagents, comparison also is made with the rate constants for the (6s) and (6s') resonance states and the (6p) states of Xe; the latter have nearly the same energy as the Kr(5s) resonance state.
Keywords:NOBLE-GAS ATOMS;MULTIPHOTON IONIZATION;PRODUCT DISTRIBUTIONS;CONTAINING MOLECULES;KRYPTON;XE;KR;EXCITATION;MIXTURES;XENON