Vibrational population distributions from rare gas halide spectra

Mechanism of vibrational relaxation and intersystem crossing within excited ion-pair states of I2

“…A'(2,): The RKR potential for A'(2.) (Tellinghuisen 1982) was fitted by a Morse potential at short range (r < 3" The inversion technique has been described elsewhere (Johnson et al 1983). Briefly, vibrational population corresponding to the best fit of experimental and calculated spectra is sought, using multiple linear regression.…”

“…In this paper we report a study of the effect of argon pressure on the UV and visible emission spectrum of I2 following excitation by ArF exc~mer laser radiation; 193 nm. Spectra were analysed by simulations and the inversion technique (Johnson et al 1983) to obtain vibrational populations in ion-pair states. Results are discussed in terms of mechanism of relaxation within the cluster of ion-pair states.…”

Reactions of Xe(3 P 2) and Xe(3 P 1) with HCl, HBr and HI; energy utilization, energy disposal, product rotational polarization and reaction dynamics

“…The intensities were measured using photon counting techniques and stored on a microcomputer data acquisition system. The data were averaged at 50 cm-1 intervals for subsequent analysis using the direct inversion procedure described elsewhere [12]. This generated vibrational population histograms for the vibrational energy disposal in the fluorescent rare gas halide products XeX(B( 89 Experimental conditions that effectively precluded significant relaxation of the nascent distributions were readily maintained since the energy available for distribution is relatively low (typically < 35 kJ mol-t) so that only low vibrational levels of the product are populated and at pressures of argon < 130 Pa, the relaxation times from these levels are long compared to the fluorescence lifetimes of the rare gas halides [16].…”

“…Tamagake, Setser and Kolts estimated the total available energy from the short wavelength limit, )~min of the fluorescence spectrum and employed spectral simulation techniques to estimate the vibrational population distributions and energies from the oscillatory fluorescence continua [10]. An alternative method employed here uses a direct inversion procedure [12] to determine the vibrational energy disposal, and surprisal analysis to estimate the energies of the highest populated levels Ge(vmax). Self-consistency can be checked by subtracting the maximum vibrational energy from the total energy hs ----Ge(vmax) = Te(XeX* )…”