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1.
Rev Sci Instrum ; 91(4): 045120, 2020 Apr 01.
Article in English | MEDLINE | ID: mdl-32357726

ABSTRACT

We describe a new tunable diode laser (TDL) absorption instrument, the Chicago Water Isotope Spectrometer, designed for measurements of vapor-phase water isotopologues in conditions characteristic of the upper troposphere [190-235 K temperature and 2-500 parts per million volume (ppmv) water vapor]. The instrument is primarily targeted for measuring the evolving ratio of HDO/H2O during experiments in the "Aerosol Interaction and Dynamics in the Atmosphere" (AIDA) cloud chamber. The spectrometer scans absorption lines of both H2O and HDO near the 2.64 µm wavelength in a single current sweep, increasing the accuracy of isotopic ratio measurements. At AIDA, the instrument is configured with a 256-m path length White cell for in situ measurements, and effective sensitivity can be augmented by enhancing the HDO content of chamber water vapor by an order of magnitude. The instrument has participated to date in the 2012-2013 IsoCloud campaigns studying isotopic partitioning during the formation of cirrus clouds and in the AquaVIT-II instrument intercomparison campaign. Realized precisions for 1-s measurements during these campaigns were 22 ppbv for H2O and 16 ppbv for HDO, equivalent to relative precisions of less than 0.5% for each species at 8 ppmv water vapor. The 1-s precision of the [HDO]/[H2O] ratio measurement ranged from 1.6‰ to 5.6‰ over the range of experimental conditions. H2O measurements showed agreement with calculated saturation vapor pressure to within 1% in conditions of sublimating ice and agreement with other AIDA instruments (the AIDA SP-APicT reference TDL instrument and an MBW 373LX chilled mirror hygrometer) to within 2.5% and 3.8%, respectively, over conditions suitable for all instruments (temperatures from 204 K to 234 K and H2O content equivalent to 15-700 ppmv at 200 hPa).

2.
Rev Sci Instrum ; 82(9): 094103, 2011 Sep.
Article in English | MEDLINE | ID: mdl-21974602

ABSTRACT

A large pulsed-beam, Fourier transform microwave spectrometer employing 48 in. diameter mirrors and 35(") (NHS-35) diffusion pump has been constructed at the University of Arizona. The Fabry-Perot-type cavity, using the large mirrors provides Q-values in the 15,000 to 40,000 range. Test spectra were obtained using transverse and coaxial injection of the pulsed-nozzle molecular beams. The measured molecular resonance linewidths were 8 kHz for the transverse injection and 2 kHz for coaxial molecular beam injection. Good signal to noise ratios were obtained for the test signals. Strong lines for butadiene iron tricarbonyl were seen with a single beam pulse (S/N = 5/1). Transitions were measured as low as 900 MHz and some previously unresolved hyperfine structure is now resolved for the butadiene iron tricarbonyl spectra. The spectrometer is operated using a personal computer with LABVIEW programs, with provisions for automatic frequency scanning. The extended, low-frequency range of this spectrometer should make it very useful for making measurements on significantly larger molecules and complexes than have been previously studied. The improved resolution, in the coaxial beam mode, will allow better resolution of hyperfine structure. The large diffusion pump allows a higher beam pulse frequency to compensate for the generally lower sensitivity at lower frequencies.

3.
J Chem Phys ; 135(15): 154304, 2011 Oct 21.
Article in English | MEDLINE | ID: mdl-22029310

ABSTRACT

Microwave spectra of the propiolic acid-formic acid doubly hydrogen bonded complex were measured in the 1 GHz to 21 GHz range using four different Fourier transform spectrometers. Rotational spectra for seven isotopologues were obtained. For the parent isotopologue, a total of 138 a-dipole transitions and 28 b-dipole transitions were measured for which the a-dipole transitions exhibited splittings of a few MHz into pairs of lines and the b-type dipole transitions were split by ~580 MHz. The transitions assigned to this complex were fit to obtain rotational and distortion constants for both tunneling levels: A(0+) = 6005.289(8), B(0+) = 930.553(8), C(0+) = 803.9948(6) MHz, Δ(0+)(J) = 0.075(1), Δ(0+)(JK) = 0.71(1), and δ(0+)(j) = -0.010(1) kHz and A(0-) = 6005.275(8), B(0-) = 930.546(8), C(0-) = 803.9907(5) MHz, Δ(0-)(J) = 0.076(1), Δ(0-)(JK) = 0.70(2), and δ(0-)(j) = -0.008(1) kHz. Double resonance experiments were used on some transitions to verify assignments and to obtain splittings for cases when the b-dipole transitions were difficult to measure. The experimental difference in energy between the two tunneling states is 291.428(5) MHz for proton-proton exchange and 3.35(2) MHz for the deuterium-deuterium exchange. The vibration-rotation coupling constant between the two levels, F(ab), is 120.7(2) MHz for the proton-proton exchange. With one deuterium atom substituted in either of the hydrogen-bonding protons, the tunneling splittings were not observed for a-dipole transitions, supporting the assignment of the splitting to the concerted proton tunneling motion. The spectra were obtained using three Flygare-Balle type spectrometers and one chirped-pulse machine at the University of Virginia. Rotational constants and centrifugal distortion constants were obtained for HCOOH···HOOCCCH, H(13)COOH···HOOCCCH, HCOOD···HOOCCCH, HCOOH···DOOCCCH, HCOOD···DOOCCCH, DCOOH···HOOCCCH, and DCOOD···HOOCCCH. High-level ab initio calculations provided initial rotational constants for the complex, structural parameters, and some details of the proton tunneling potential energy surface. A least squares fit to the isotopic data reveals a planar structure that is slightly asymmetric in the OH distances. The formic OH···O propiolic hydrogen bond length is 1.8 Å and the propiolic OH···O formic hydrogen bond length is 1.6 Å, for the equilibrium configuration. The magnitude of the dipole moment was experimentally determined to be 1.95(3) × 10(-30) C m (0.584(8) D) for the 0(+) states and 1.92(5) × 10(-30) C m (0.576(14) D) for the 0(-) states.


Subject(s)
Alkynes/chemistry , Formates/chemistry , Propionates/chemistry , Protons , Dimerization , Hydrogen Bonding , Microwaves
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