The spin-forbidden a 4Σ--X 2Π1/2 transition of GeH detected in absorption using intracavity laser spectroscopy

The a (4)Sigma(-)-X-2 Pi(1/2) transition ofGeHhas been recorded in absorption for the first time using Intracavity Laser Spectroscopy (ILS). The GeH molecules were produced in a 0.40-0.60 A DC plasma discharge inside an aluminum hollow cathode, using 500 mTorr of Ar, 100 mTorr of H-2, and 200 mTorr of GeH4. This cathode is located within the resonator cavity of a Coherent Verdi (TM) V-10 pumped dye laser. Effective path lengths for this series of measurements using the ILS method ranged from 2 to 7 km. Spectra were calibrated using the absorption spectrum of I-2 collected from an extracavity cell, the I-2 transmission spectrum from Salami and Ross, J. Mol. Spectrosc. 223(1), 157 (2005) and PGOPHER's [C.M. Western, J. Quant. Spectrosc. Radiat. Transfer 186, 221-242 (2016)] calibration feature. Differences in peak positions between calibrated experimental spectra and the reference data were on average less than +/- 0.002 cm(-1). All eight branches expected to have appreciable intensity for the transition have been identified, and isotopologue splitting was observed in features of 5 of the 8 identified rotational branches. Molecular constants have been obtained for the a (4)Sigma(-) states of (GeH)-Ge-70 (20.84% abundant), (GeH)-Ge-72(27.54% abundant), and (GeH)-Ge-74(36.28% abundant). The transitions were fit using PGOPHER, holding the ground state constants fixed to the values reported by Towle and Brown [Mol. Phys. 78(2), 249 (1993)]. The constants for the a (4)Sigma(-) state of 74GeH determined by the fit are T-0 = 16 751.5524(13) cm(-1), B-0 = 6.764 912(33) cm(-1), D-0 = 0.459 60(17) x 10(-3) cm 1, lambda(SS) = 9.7453(12) cm(-1), lambda(D) = 0.468(14) x 10(-3) cm 1, gamma = 0.077 878(84), and gamma(S) = 0.361(77) x 10(-3) cm(-1). Published by AIP Publishing.