Rotationally resolved ground state vibrational levels of HC2S studied by two-color resonant four-wave mixing

J Phys Chem A. 2010 Mar 11;114(9):3329-33. doi: 10.1021/jp909738n.

Abstract

A high-resolution study of the X(2)Pi(3/2) ground state rovibronic energy levels of jet-cooled HC(2)S radical using the double-resonance two-color four-wave mixing technique (TC-RFWM) is reported. The rotational structure of the bands is observed by excitation of selected R-branch lines in the origin band of the A(2)Pi(3/2)-X(2)Pi(3/2) electronic system. The second laser frequency is scanned to transfer the population from the rotational level(s) of the upper state to selected vibronic levels of the ground state. Fourteen rotationally resolved vibrational bands have been recorded for energies up to 1800 cm(-1) above the v'' = 0 X(2)Pi(3/2) electronic ground state. Effective rotational constants and origins are determined for levels that involve fundamental and overtone combinations of the nu(3) (CS stretch), nu(4) (CCH bend), and nu(5) (CCS bend) vibrations. This illustrates the power and advantages of the TC-RFWM approach for the study of the ground state manifold of reactive intermediates produced in low concentrations with high resolution, good signal-to-noise and wide dynamic range.