[Vibration-vibration energy transfer between highly vibrational excited RbH and H2, N2]

Rb-H2 mixture was irradiated with pulses of 696.4 nm radiation from a OPO laser, populating 6D state by two-photon absorption. The vibrational levels of RbH(X1sigma+,v" = 0-2) generated in the reaction of Rb(6D) with H2. Vibrational-state-specific total-removal relaxation rate coefficients, k(v) (M), for RbH(X1sigma+, v" = 15-22) by M = H2 and N2 were investigated in a pump and probe configuration. By the overtone pumping with a cw diode laser, highly vibrational states v" = 15-22 of RbH in its ground electronic state were obtained. Another diode laser was used to probe the prepared vibrational state. The decay signal of laser induced time-resolved fluorescence from A 1sigma+ (v') --> X1sigma+ (v") transition was monitored. Based on the Stern-Volmer equation, the total relaxation rate coefficient k(v) (H2) were yielded. A plot of k(v) (H2 + N2) vs alpha (mole fraction H2) yields a line with a slope of k(v) (H2)-k(v) (N2) and an intercept of k(v) (N2). The values of k(v) (H2) obtained from the slope of the fitted lines compare well with determined values of the k(v) (H2) from the Sern-Volmer plots. At v" < 18, the rate coefficients k(v) (M) increases linearly with vibrational quantum number. This linear region is dominated by single quantum relaxation (deltav = 1) collisional propensity rules. The region (v" > or = 18) where the dependence is much stronger than linear shows significant contribution from multiquantum (deltav > or = 2) relaxation or resonant vibration-vibration energy transfer between highly vibrationally excited RbH and H2 or N2. For RbH(v") + N2 (0), we measured the time-profile of v" = 16 after preparation of v" = 21. A clear bimodal distribution was observed. The first peak is due to resonant vibration-vibration energy transfer: RbH (v" = 21) + N2 (0) --> RbH (v" = 16) + N2 (1). The much broader second peak, at longer time delays, is due to sequential single-quantum relaxation. Although the second process results in a distribution that is much more spread out in time, the peak height is in the same order of magnitude, indicating that the two processes are at least comparable in probability.