FLUORESCENCE-DETECTED INFRARED-ULTRAVIOLET AND RAMAN-ULTRAVIOLET DOUBLE-RESONANCE IN ACETYLENE GAS - STUDIES OF SPECTROSCOPY AND ROTATIONALENERGY-TRANSFER

Fluorescence-detected Raman-ultraviolet and infrared-ultraviolet doubl e resonance (DR) spectroscopy enables state-selective studies of rotat ional and vibrational energy transfer in gas-phase acetylene (C2H2) an d its deuterated isotopomers (C2HD, C2D2). The Raman-UV DR approach en tails pulsed coherent Raman excitation in the nu(2) rovibrational band of C2H2(g), followed by fluorescence-detected rovibronic probing of t he resulting rovibrational population distributions. Corresponding IR- UV DR experiments employ a line-tunable, pulsed CO2 laser to excite ro vibrational transitions in the 2 nu(4) band of C2HD(g) and in the (nu( 4) + nu(5)) band of C2D2(g), with similar fluorescence-detected rovibr onic probing. These time-resolved DR spectroscopic techniques provide rotationally specific information on collision-induced molecular energ y transfer in acetylene. This paper extends previous Raman-UV DR spect roscopic studies of C2H2 and presents fresh IR-UV DR spectra of gas-ph ase C2HD and C2D2, including evidence of a novel two-step excitation s equence in which a single CO2-laser pulse promotes C2D2 by successive transitions in the (nu(4) + nu(5)) and (2 nu(4) + 2 nu(5) - nu(4) - nu (5)) absorption bands. Kinetic measurements and mechanistic observatio ns are also reported for collision-induced rotational energy transfer in acetylene gas, complementing other investigations of rotationally r esolved vibrational energy transfer.