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Owing to its unparalleled structural specificity, rotational spectroscopy is a powerful technique to unambiguously identify and characterize volatile, polar molecules. We present here a new experimental approach, automated microwave double resonance (AMDOR) spectroscopy, to rapidly determine the rotational constants of these compounds without a priori knowledge of elemental composition or molecular structure. This task is achieved by rapidly acquiring the classical (frequency vs. intensity) broadband spectrum of a molecule using chirped-pulse Fourier transform microwave (FTMW) spectroscopy and subsequently analyzing it in near real-time using complementary cavity FTMW detection and double resonance. AMDOR measurements provide a unique "barcode" for each compound from which rotational constants can be extracted. To illustrate the power of this approach, AMDOR spectra of three aroma compounds - trans-cinnamaldehyde, α-, and β-ionone - have been recorded and analyzed. The prospects to extend this approach to mixture characterization and purity assessment are described. [ABSTRACT FROM AUTHOR]

HOCO is an important intermediate in combustion and atmospheric processes because the OH + CO → H + CO2 reaction represents the final step for the production of CO2 in hydrocarbon oxidation, and theoretical studies predict that this reaction proceeds via various intermediates, the most important being this radical. Isotopic investigations of trans- and cis-HOCO have been undertaken using Fourier transform microwave spectroscopy and millimeter-wave double resonance techniques in combination with a supersonic molecular beam discharge source to better understand the formation, chemical bonding, and molecular structures of this radical pair. We find that trans- HOCO can be produced almost equally well from either OH + CO or H + CO2 in our discharge source, but cis-HOCO appears to be roughly two times more abundant when starting from H + CO2. Using isotopically labelled precursors, the OH + C18O reaction predominately yields HOC18O for both isomers, but H18OCO is observed as well, typically at the level of 10%-20% that of HOC18O; the opposite propensity is found for the 18OH + CO reaction. DO + C18O yields similar ratios between DOC18O and D18OCO as those found for OH + C18O, suggesting that some fraction of HOCO (or DOCO) may be formed from the back-reaction H + CO2, which, at the high pressure of our gas expansion, can readily occur. The large 13C Fermi-contact term (aF) for trans- and cis-HO13CO implicates significant unpaired electronic density in a σ-type orbital at the carbon atom, in good agreement with theoretical predictions. By correcting the experimental rotational constants for zero-point vibration motion calculated theoretically using second-order vibrational perturbation theory, precise geometrical structures have been derived for both isomers. [ABSTRACT FROM AUTHOR]

The rotational spectra of two small silicon sulfides, silanethione H2SiS and the disilicon sulfide ring Si2S, have been detected in the centimeter band by Fourier transform microwave spectroscopy of a molecular beam; lines of H2SiS were also observed in the millimeter band up to 377 GHz in a glow discharge. Precise rotational and centrifugal distortionconstants have been determined for the normal and a number of the more abundant rare isotopic species of both closed-shell molecules. Theoretical equilibrium (re) structures of H2SiS and Si2S were derived from coupled-cluster calculations that included triple and quadruple excitations, core correlation, and extrapolation to the basis-set limit. The re structures agree to within 5×10-4 Å and 0.1°with empirical equilibrium (reemp) structures derived from the experimental rotational constants, combined with theoretical vibrational and electronic corrections. Both H2SiS and Si2S are good candidates for radioastronomical detection in the circumstellar shells of evolved carbon-rich stars such as IRC+10216, because they are fairly polar and are similar in composition to the abundant astronomical molecule SiS. [ABSTRACT FROM AUTHOR]

The rotational spectra of five weakly bonded hydrogen-OCS complexes (paraH2, orthoH2, HD, orthoD2, and paraD2) are measured. Hyperfine structure is resolved and analyzed in all except the complex with paraH2, where I=0. For the two j=1 species, orthoH2-OCS and paraD2-OCS, nuclear hyperfine coupling constants are found to be da=21.2(2) and 8.4(2) kHz, respectively, indicative of nearly free uniaxial rotation of the hydrogen around the b-inertial axis. Similar analyses for HD-OCS and orthoD2-OCS yield the quadrupole coupling constants eqQa=16(2) and 30(2) kHz, respectively, showing that the internal rotational motions of HD and orthoD2 in the complex are slightly hindered producing a small nonspherical distribution. For orthoD2-OCS, the observed hyperfine structure indicates that the nuclear spin states I=0 and 2 are strongly coupled in the rotation of the complex. [ABSTRACT FROM AUTHOR]

On the basis of extensive coupled cluster calculations, the rotational spectra of the linear silicon- and sulfur-containing carbon chains SiC[sub 2n] S (n = 1 -3) in their singlet electronic ground state and SiC[sub 3]S in its triplet electronic ground state have been detected and characterized by means of molecular beam Fourier transform microwave spectroscopy. Rotational and centrifugal distortion constants have been determined to high accuracy as well as the spin-spin coupling constant for triplet SiC[sub 3] S. In addition, the [sup 29]Si, [sup 34]S, and both [sup 13]C isotopic species of SiC[sub 2]S have been detected, allowing the determination of both an effective r[sub 0] structure, as well as a mixed experimental-theoretical structure resulting from the combination of the measured rotational constants with the vibrationrotation coupling constants calculated ab initio. Several rotational satellite lines have also been observed for SiC[sub 2]S and, on the basis of their predicted vibration-rotation and l-type doubling constants, were assigned to the two highest-frequency stretching modes υ[sub 1] and υ[sub 2], and to a progression in the second lowest-frequency bending mode υ 4 up to 3 υ 4. Equilibrium structures and various spectroscopic properties are predicted for all SiC[sub n]S species with n = 1 - 8. [ABSTRACT FROM AUTHOR]

Uses the sideband optical-optical double resonance Zeeman effect spectroscopy to study the electronic spectrum of the gas-phase platinum-hydrogen compound. Analysis of the sub-Doppler Zeeman spectrum of each feature using a systematic quasi-two-dimensional approach; Radio frequency magnetic resonances.

Applies the sideband optical-optical double resonance Zeeman effect spectroscopy to study transition metal hydrides. Resolution of the extremely small ground state photon hyperfine splittings; Record of the sub-dopper spectra; Deviation of the g values in each state from the nominal Hund's coupling case.

Several variants of the one-laser, two-color technique of sideband optical–optical double resonance Zeeman (SOODRZ) spectroscopy, which enables Zeeman and hyperfine splittings to be measured at sub-Doppler resolution, are described; a detailed theory of the line shape and signal-to-noise ratio for each variant is also presented. In the single-frequency variant of SOODRZ spectroscopy, radio frequency sidebands are imposed onto a single-frequency continuous wave laser beam to determine energy splittings between pairs of closely spaced levels. Each pair of closely spaced levels is coupled to a third isolated level by optical transitions and is tuned into resonance by the Zeeman effect. A theoretical treatment of the SOODRZ effect is presented here. It is shown that both the real and imaginary contributions to the complex third-order optical susceptibility tensor χ(3) can be observed and that the SOODRZ signal originates from a cross term between the amplitude of the unperturbed frequency-modulated beam of the laser and the nonlinear signal amplitude Re{EL*·ENL}. The SOODRZ signal is directly proportional to ΔNμ4MI20 (where M is the modulation index), rather than (ΔN)2, μ8, and I30 as in degenerate four-wave mixing and other nonlinear spectroscopies, which means the detection sensitivity of SOODRZ spectroscopy is considerably higher for low laser intensities and at lower number densities.Moreover, the linewidth of the sub-Doppler feature is independent of the both the Doppler width of the optical transition and the natural width of the common linked level and, hence, is immune from the effects such as upper state predissociation. Two different types of modulators, acousto-optic and electro-optic, can be used in the single-frequency variant of SOODRZ spectroscopy. The unique features of SOODRZ schemes incorporating both types of modulators are described. SOODRZ spectroscopy can also be performed with a multimode broadband... [ABSTRACT FROM AUTHOR]

The application of magnetic rotation spectroscopy (MRS) to the electronic spectra of gas phase NiH and CeF is examined. Experimental results for both MRS and laser excitation spectroscopy are presented for the NiH B 2Δ5/2–X 2Δ5/2 (1,0) and 2[uppercase_phi_synonym]7/2–X 2Δ5/2 (0,0) bands. A comparison between these two techniques clearly illustrates the ability of MRS to simplify and presort spectra. The power of MRS originates from its specificity for low-J, ΔΩ=ΔJ transitions and its ability, based on the sign and magnitude of the MRS effect, to partially presort rotational branches. A simple theoretical explanation of the MRS results, based on the structure of the underlying Zeeman pattern, is presented. Also, the extension of MRS to the more complicated and congested spectrum of CeF is presented. Using MRS, a previously unassigned CeF band, near 568 nm, has been definitively assigned as Ω’=4.5←Ω‘=3.5. [ABSTRACT FROM AUTHOR]