RESUMO
The high-resolution infrared spectrum of isoprene has been observed under supersonic jet-cooled conditions in the region of the ν26 vibrational band near 992 cm-1. The spectrum was assigned and fit using a standard asymmetric top Hamiltonian, and an acceptable fit was obtained for transitions to excited state energy levels with J ≤ 6, with an error in the fit of 0.002 cm-1. For excited state energy levels with J > 6, a perturbation was present that prevented fitting using the standard asymmetric top Hamiltonian. Based on previous anharmonic frequency calculations and observed vibrational bands of isoprene, the perturbation is most likely caused by Coriolis coupling between the ν26 and ν17 vibrations or a combination band that lies near the ν26 band. The excited state rotational constants from the fit show reasonable agreement with previous anharmonic calculations performed at the MP2/cc-pVTZ level of theory. The jet-cooled spectrum is compared with previous high-resolution measurements of this band at room temperature and shows that understanding the perturbation will be necessary to accurately model this vibrational band.
RESUMO
High-resolution spectra of the intramolecular bending modes of deuterated water dimer, (D2O)2, have been measured using a quantum cascade laser based cavity ringdown spectrometer. Two perpendicular bands have been observed and are assigned as the K(a) = 1 â 0 and K(a) = 2 â 1 bands of the bending mode of the hydrogen bond donor. The tunneling splittings in the complex are well-resolved, and it is found that excitation of the donor bend has little effect on tunneling of the hydrogen bond acceptor, but causes significant perturbations on the tunneling motion which exchanges the roles of hydrogen bond donor and acceptor. The presence of this perturbation has prevented a detailed assignment of the tunneling levels in the excited state at this time. An accurate value for the band center of the donor bend is calculated to be 1182.2 cm(-1), which is in good agreement with previous theoretical calculations performed on an ab initio potential energy surface.
RESUMO
A new instrument has been constructed that couples a supersonic expansion source to a continuous wave cavity ringdown spectrometer using a Fabry-Perot quantum cascade laser (QCL). The purpose of the instrument is to enable the acquisition of a cold, rotationally resolved gas phase spectrum of buckminsterfullerene (C(60)). As a first test of the system, high resolution spectra of the nu(8) vibrational band of CH(2)Br(2) have been acquired at approximately 1197 cm(-1). To our knowledge, this is the first time that a vibrational band not previously recorded with rotational resolution has been acquired with a QCL-based ringdown spectrometer. 62 transitions of the three isotopologues of CH(2)Br(2) were assigned and fit to effective Hamiltonians with a standard deviation of 14 MHz, which is smaller than the laser frequency step size. The spectra have a noise equivalent absorption coefficient of 1.4 x 10(-8) cm(-1). Spectral simulations of the band indicate that the supersonic source produces rotationally cold (approximately 7 K) molecules.