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Isofulminic acid, HONC, the most energetic stable isomer of isocyanic acid HNCO, higher in energy by 84 kcal/mol, has been detected spectroscopically by rotational spectroscopy supported by coupled cluster electronic structure calculations. The fundamental rotational transitions of the normal, carbon-13, oxygen-18, and deuterium isotopic species have been detected in the centimeter band in a molecular beam by Fourier transform microwave spectroscopy, and rotational constants and nitrogen and deuterium quadrupole coupling constants have been derived. The measured constants agree well with those predicted by ab initio calculations. A number of other electronic and spectroscopic parameters of isofulminic acid, including the dipole moment, vibrational frequencies, infrared intensities, and centrifugal distortion constants have been calculated at a high level of theory. Isofulminic acid is a good candidate for astronomical detection with radio telescopes because it is highly polar and its more stable isomers (HNCO, HOCN, and HCNO) have all been identified in space. [ABSTRACT FROM AUTHOR]

The technique of frequency-modulation enhanced magnetic rotation spectroscopy (FM-MRS) is applied here to the study of the electronic spectra of gas-phase transition metal hydrides and deuterides. Experimental FM-MR results for several bands of PdH, PdD, NiH, and CuH are presented. In the case of PdH, an Ω=0.5–XΩ=0.5 band at 4371 Å has been observed and assigned. Prior to this work, although several bands of PdD had been reported previously, no electronic transitions of PdH had been assigned. All of the PdH, PdD, and NiH bands studied in the 4200–4600 Å wavelength region are strongly predissociated, and in the case of PdH and PdD, strongly and multiply perturbed as well. [ABSTRACT FROM AUTHOR]

The technique of frequency-modulation enhanced magnetic rotation spectroscopy (FM-MRS) is described. An experimental comparison between FM-MRS, frequency-modulation, and magnetic rotation spectroscopies clearly demonstrates that the double null absorption-based FM-MR technique is more sensitive than either FM or MRS separately. The theoretical basis for this sensitivity enhancement can be attributed to a 1/θ (where θ is the small uncrossing angle between two nearly crossed polarizers) improvement in the sensitivity of the combined FM-MR technique relative to that of standard FM spectroscopy. The sensitivity improvement of FM-MRS relative to MRS is even better than that for FM spectroscopy. In practical terms, this enhancement can improve the experimentally achievable sensitivity of FM and magnetic rotation spectroscopies by factors of O(101) to O(102) and O(102) to O(104), respectively, levels that approach the theoretical quantum noise limit. In addition, because FM-MRS is based on the Zeeman effect, Zeeman information is encoded into FM-MR line profiles in the form of relative phase labels and line shapes. The relative phases and line shapes of rotational lines can be used to group features by rotational branch and to differentiate between magnetically active (Λ≠0, Σ≠0) and inactive (Λ=0, Σ=0) features. The theory of FM-MRS, including a discussion of line shapes and a sensitivity analysis, is reviewed here; applications of the FM-MR technique are presented separately in the following paper. [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]