R. A. Provencal

Infrared cavity ringdown spectroscopy of methanol clusters: Single donor hydrogen bonding

Infrared cavity ringdown laser absorption spectroscopy has been used to study the O–H stretching vibrations of jet-cooled methanol clusters in direct absorption. Rovibrational bands for (CH3OH)2, (CH3OH)3, and (CH3OH)4 have been measured. Both bonded and free O–H stretches were measured for the dimer, indicating that its structure is linear. Five bands were assigned to the methanol trimer, indicating the presence of a second cyclic isomer in the molecular beam. A detailed study of the free O–H stretching region shows that methanol clusters larger than dimer must exist in cyclic ring configurations. In order to facilitate spectral assignment, harmonic frequencies and infrared intensities were calculated for the methanol monomer, dimer, and trimer with second order Mo/ller–Plesset perturbation theory. Using the theoretical infrared intensities and measured vibrational band absorptions, absolute cluster concentrations were calculated. Results agree with previous experimental and theoretical work.

Infrared cavity ringdown spectroscopy of water clusters: O–D stretching bands

The infrared O–D stretching spectrum of fully deuterated jet-cooled water clusters is reported. Sequential red-shifts in the single donor O–D stretches, which characterize the cooperative effects in the hydrogen bond network, were accurately measured for clusters up to (D2O)8. Detailed comparisons with corresponding data obtained for (H2O)n clusters are presented. Additionally, rotational analyses of two D2O dimer bands are presented. These measurements were made possible by the advent of infrared cavity ringdown laser absorption spectroscopy (IR-CRLAS) using Raman-shifted pulsed dye lasers, which creates many new opportunities for gas phase IR spectroscopy.

Interstellar Detection of CCC and High-Precision Laboratory Measurements near 2 THz

We describe more fully our original tentative interstellar detection of the triatomic pure carbon chain molecule, CCC, in absorption toward the Galactic center source Sgr B2. C3 was detected with the Kuiper Airborne Observatory (KAO) by observing the R(2) bending vibration-rotation transition (0, 1 1 ,0 0, 0 0 , 0) near 65.7 cm 1 during one ) R ( of the last flights of KAO. The R(2) absorption line detected toward Sgr B2 is centered at 63.7(5) km s 1 , with km s 1 and a peak absorption of 18(3)%. This original tentative interstellar detection of C 3 DV(FWHM)p 8.3(9) has recently been confirmed by J. Cernicharo et al. through observation of a total of nine absorption lines, including the same R(2) line with the Infrared Space Observatory . We also present highly precise new laboratory measurements of 10 rovibrational transition frequencies of the n2 bending mode of C3, which have been obtained with the Cologne Sideband Spectrometer for Terahertz Application. Subject headings: ISM: individual (Sagittarius B2) — ISM: molecules — line: identification — methods: laboratory — techniques: spectroscopic On-line material: color figure

High resolution pulsed infrared cavity ringdown spectroscopy: Application to laser ablated carbon clusters

We report the design and performance of a tunable, pulsed high resolution mid infrared cavity ringdown spectrometer. Stimulated Raman scattering in H2/D2 is used to downconvert the output of a SLM Alexandrite ring laser (720–800 nm) to the mid infrared (3–8 μm). The infrared frequency bandwidth was determined to be 90±5 MHz from measurements of Doppler broadened OCS transitions at 5 μm. The minimum detectable per pass fractional absorption is 1 ppm. We observe a frequency dependent ringdown cavity transmission of ±5 ppm due to spatial variations of the mirror reflectivity. The υ6 band of linear C9 formed by laser ablation of graphite in a He molecular beam was measured, showing a factor of 2 improvement in sensitivity relative to previous IR diode laser experiments. Based on calculated IR intensities, the number density of C9 in the molecular beam is 1.3*1011 molec/cm3 and the minimum detectable density is 1*109 molec/cm3. We expect this spectrometer to be a powerful tool for the study of transient specie...