Vibrational and rotational energy transfers involving the CH B 2Sigma(-) v=1 vibrational level in collisions with Ar, CO, and N2O.
With photolysis-probe technique, we have studied vibrational and rotational energy transfers of CH involving the B (2)Sigma(-) (v=1, 0<or=N<or=6, F) state by collisions with Ar, CO, and N(2)O. For the vibrational energy transfer (VET) measurements, the time-resolved fluorescence of the B-X(0,0) band is monitored following the (1,0) band excitation. For the rotational energy transfer (RET) measurements, the laser-induced fluorescence of the initially populated state is dispersed using a step-scan Fourier transform spectrometer. The time-resolved spectra obtained in the nanosecond regime may yield the RET information under a single pressure of the collider. The rate constants of intramolecular energy transfers are evaluated with simulation of kinetic models. The VET lies in the range of 4x10(-12) to 4x10(-11) cm(3) molecule(-1) s(-1), with efficiency following the order of Ar<CO<N(2)O, reflecting the average over Boltzmann rotational distribution. The RET rates are more rapid by one to two orders of magnitude, comparable to the gas kinetic, with the trend of Ar<CO<N(2)O. The transfer rates decrease with increasing N and DeltaN, proceeding via the DeltaN=-1 transitions slightly larger than DeltaN=+1. With the fine-structure labels resolved up to N=6, the fine-structure-conserving collisions prevail increasingly with increasing N in DeltaN not equal 0. The rate constants for the F(2)-->F(1) transitions are larger than the reverse F(1)-->F(2) transitions in DeltaN=0 for the Ar and CO collisions. The trend of fine-structure conservation is along the order of N(2)O<CO approximately Ar. For the CH-Ar collisions, the fine-structure conservation is less pronounced as compared with the v=0 level reported previously. In general, the propensity rules obeyed in the v=0 collision with Ar are valid in v=1, but the latter case shows a weaker tendency. It might be caused by the anisotropy difference of interaction potential when vibrational excitation is considered. For the polyatomic collider, the strong long-range dipole-dipole interaction may have the chance to vary the rotational orientation to increase the fine-structure-changing transitions.
Huang
Hong-Yi
HY
Department of Chemistry, National Taiwan University, Taipei 106 and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan.
Tsai
Ming-Tsang
MT
Lin
King-Chuen
KC