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Motivated by our recent finding that the singlet-triplet bands of selenoformaldehyde involve an upper state with large zero field splittings, we have extended the theory and written a program for predicting and fitting such rotationally resolved spectra. Triplet state matrix elements for a case ͑A͒ basis have been developed, including corrections for centrifugal and spin-centrifugal distortion. The full Hamiltonian matrix has been symmetry adapted, simplifying the problem to four individual matrices of approximately equal size for molecules of orthorhombic symmetry. Diagonalization of these matrices yields triplet state energies that are in agreement with previous treatments using a basis in which the spin splittings are small relative to the rotational intervals. Methods have been developed for sorting the eigenvalues and assigning quantum labels regardless of the magnitude of the spin splittings. The calculation of the relative intensities of the rotational lines within a band has been programmed using transition moment matrix elements from the literature. The selection rules for various upper state symmetries have been developed in a form useful for the analysis of spectra. Band contour predictions of spectra for various coupling cases have been presented.

Using the technique of single vibronic level emission spectroscopy, the ground state vibrational manifolds of jet-cooled HSiF and DSiF have been studied. The radicals were produced in a pulsed electric discharge jet using trifluorosilane (HSiF3 or DSiF3) as the precursor. The gas phase ground state harmonic vibrational frequencies of both isotopomers have been determined for the first time. A normal coordinate analysis using the vibrational frequencies and literature values for the centrifugal distortion constants allowed the determination of all six ground state force constants. Our previous ground state rotational constants have been combined with the calculated harmonic contributions to the α constants to obtain an average (rz) structure and an estimate of the equilibrium (rez) structure. The reliability of the force constants has been evaluated by Franck–Condon simulations of the emission spectra and comparisons of the calculated and experimentally determined inertial defects.

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Among the most important of chemical intermediates are the carbenes, characterized by a divalent carbon that generates low-lying biradical (triplet) and spin-paired (singlet) configurations with unique chemical reactivities. The "holy grail" of carbene chemistry has been determining the singlet-triplet gap and intersystem crossing rates. We report here the first high resolution spectra of singlet-triplet transitions in a prototypical singlet carbene, CHCl, which probe in detail the triplet state structure and spin-orbit coupling with the ground singlet state. Our spectra reveal a pronounced vibrational state dependence of the triplet state spin-spin splitting parameter, which we show is a sensitive probe of spin-orbit coupling with nearby singlet states. The parameters derived from our spectra, including a precise determination of the singlet-triplet energy gap, are in excellent agreement with recent ab initio calculations.