INFRARED-ULTRAVIOLET DOUBLE-RESONANCE MEASUREMENTS ON THE TEMPERATURE-DEPENDENCE OF ROTATIONAL AND VIBRATIONAL SELF-RELAXATION OF NO(X(2)PI, UPSILON=2,J)

Infrared-ultraviolet double resonance experiments have been performed to measure the rates of rotational and vibrational self-relaxation in NO at three temperatures: 295 K, 200 K, and 77 K. Pulses of tunable in frared radiation from an optical parameteric oscillator have been used to excite molecules into selected rotational levels (j = 0.5, 6.5, or 15.5) in the \nu = 2; Omega = 1/2] vibronic component of the X(2)II e lectronic ground state of NO. Loss of population from the initially ex cited level was observed by making time-resolved laser-induced fluores cence measurements on appropriate lines in the A(2) Sigma(+) - X(2)II( 2,2) band. The rate constants for removal of population from specific rovibronic levels are essentially independent of j and at 295 K agree well with previous direct measurements on a range of nu, j levels. The rotationally thermalized population in nu = 2 relaxes by vibration-vi bration (V-V) energy exchange, NO(nu = 2) + NO(nu = 0) --> 2 NO(nu = 1 ), at a rate which is almost independent of temperature and which seem s to be uninfluenced by the presence of spin-orbit degeneracy in, and attractive forces between, the NO collision partners.