REMPI SPECTRA OF CL-2 - VIBRATIONAL AND ROTATIONAL ANALYSIS OF THE 2(1)PI(G) RYDBERG STATES OF CL-35(2), (CLCL)-CL-35-CL-37, AND CL-37(2)

Rotational contours of the (2 + 1) resonance enhanced multiphoton ioni zation (REMPI) spectra of the vibrational bands corresponding to the 2 (1) Pi(g) <-- X transitions in Cl-35(2), (ClCl)-Cl-35-Cl-37, and Cl-37 (2) for the natural abundance of isotopes have been recorded at room t emperature. Vibrational bands consist of contributions from all three isotopomers with varying degrees of overlap depending on vibrational q uantum numbers. Band heads and tails were analyzed by simulation calcu lation. Rotational constants (B-v' and D-v') and corresponding internu clear distances (r(v')) for the Rydberg state were obtained, as well a s equilibrium position rotational parameters. Thus for Cl-35(2), B-e' = 0.2763 +/- 0.0008 cm(-1), alpha(e)' = 0.0015 +/- 0.0001 cm(-1), and r(e)' = 1.868 +/- 0.005 Angstrom. Vibrational analyses based on the de termination of band origins from the spectral simulations were perform ed to obtain (omega(e) = 664.8 +/- 0.2 cm(-1) omega(e)x(e) = 2.62 +/- 0.02 cm(-1) for Cl-35(2), and T-e' = 63970 +/- 3 cm(-1). Spectroscopic parameters for (ClCl)-Cl-35-Cl-37,and Cl-37(2) are derived from those for Cl-35(2) in a standard way (see text). (C) 1996 Academic Press, I nc.