Doppler-Free Spectroscopy of Weak Transitions: An Analytical Model Applied to Formaldehyde

Experimental observation of Doppler-free signals for weak transitions can be greatly facilitated by an estimate for their expected amplitudes. We derive an analytical model which allows the Doppler-free amplitude to be estimated for small Doppler-free signals. Application of this model to formaldehyde allows the amplitude of experimentally observed Doppler-free signals to be reproduced to within the experimental error.Comment: 7 pages, 7 figures, 1 table, v2: many small improvements + corrected line assignmen

An experimental and theoretical study of the electronic spectrum of the HBCl free radical

Following our previous discovery of the spectra of the HBX (X = F, Cl, and Br) free radicals [S.-G. He, F. X. Sunahori, and D. J. Clouthier, J. Am. Chem. Soc. 127, 10814 (2005)], the A\u303(2)A(\u2033)\u3a0-X\u303(2)A(') band systems of the HBCl and DBCl free radicals have been studied in detail. The radicals have been prepared in a pulsed electric discharge jet using a precursor mixture of BCl3 and H2 or D2 in high pressure argon. Laser-induced fluorescence (LIF) and single vibronic level emission spectra have been recorded to map out the ground and excited state vibrational energy levels. The band system involves a linear-bent transition between the two Renner-Teller components of what would be a (2)\u3a0 electronic state at linearity. We have used high level ab initio theory to calculate the ground and excited state potential energy surfaces and have determined the vibronic energy levels variationally. The theory results were used to assign the LIF spectra which involve transitions from the ground state zero-point level to high vibrational levels of the excited state. The correspondence between theory and experiment, including the transition frequencies, upper state band symmetries, and H, B, and Cl isotope shifts, was used to validate the assignments

BH2 revisited: New, extensive measurements of laser-induced fluorescence transitions and ab initio calculations of near-spectroscopic accuracy

The spectroscopy of gas phase BH2 has not been explored experimentally since the pioneering study of Herzberg and Johns in 1967. In the present work, laser-induced fluorescence (LIF) spectra of the A\u303(2)B1(\u3a0u)-X\u303 (2)A1 band system of (11)BH2, (10)BH2, (11)BD2, and (10)BD2 have been observed for the first time. The free radicals were "synthesized" by an electric discharge through a precursor mixture of 0.5% diborane (B2H6 or B2D6) in high pressure argon at the exit of a pulsed valve. A total of 67 LIF bands have been measured and rotationally analyzed, 62 of them previously unobserved. These include transitions to a wide variety of excited state bending levels, to several stretch-bend combination levels, and to three ground state levels which gain intensity through Renner-Teller coupling to nearby excited state levels. As an aid to vibronic assignment of the spectra, very high level hybrid ab initio potential energy surfaces were built starting from the coupled cluster singles and doubles with perturbative triples (CCSD(T))/aug-cc-pV5Z level of theory for this seven-electron system. In an effort to obtain the highest possible accuracy, the potentials were corrected for core correlation, extrapolation to the complete basis set limit, electron correlation beyond CCSD(T), and diagonal Born-Oppenheimer effects. The spin-rovibronic states of the various isotopologues of BH2 were calculated for energies up to 22 000 cm(-1) above the X\u303 (000) level without any empirical adjustment of the potentials or fitting to experimental data. The agreement with the new LIF data is excellent, approaching near-spectroscopic accuracy (a few cm(-1)) and has allowed us to understand the complicated spin-rovibronic energy level structure even in the region of strong Renner-Teller resonances

The Renner-Teller effect in floppy chain tetra-atomic molecules

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