Lee, Timothy J.
HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.
A summary is presented of our spectroscopic survey of comets extending for roughly 19 years from 1985 to 2004 comprising data for 92 comets of which 50 showed good emissions. All data were re-analyzed using consistent reduction techniques. Our observations of comets over several apparitions and comets observed over an extended period indicate no major changes in compositional classification. To our regret, no major unidentified cometary features were found in our surveyed spectral region of 5200-10400 Å. Absolute production rates for the dominant parent molecule H 2O and the daughter species C 2, NH 2 and CN are determined within the limits of the Haser model as are values for the dust continuum, Afρ. From these data, production rate ratios are calculated for C 2/H 2O, NH 2/H 2O, CN/H 2O and Afρ/H 2O. Excluding the odd Comets Yanaka (1988r), 43P/Wolf-Harrington and 19P/Borrelly, with unusual spectra, our set of comets exhibited relatively uniform composition. Detailed analyses of our data resulted in four taxonomic classes: Comets of typical composition (˜70%); exhibiting typical ratios with respect to water of C 2, NH 2, and CN. Tempel 1 type (˜22%); having a deficiency in C 2 but normal NH 2 abundance. G-Z type (˜6%); having both low C 2 and NH 2 ratios. The unusual object Yanaka (1988r) (˜2%?); no detectable C 2 or CN emission but normal NH 2. It is uncertain whether there is a clear separation between the comets of typical composition and those with C 2 depletion, or whether the latter consists of a group showing a continuum of decreasing C 2/CN ratios. Our spectroscopic investigations result in a visual record of the various compositional classes, which are illustrated in a number of figures. Production rate comparisons with the comet photometry program of Schleicher and A'Hearn [A'Hearn, M.F., and 4 colleagues, 1995. Icarus 118, 223-270] for 13 comets in common yielded good agreement once the different scale lengths are taken into account. An