Theoretical IR spectra of ionized naphthalene.

We report the results of a theoretical study of the effect of ionization on the IR spectrum of naphthalene, using ab initio molecular orbital theory. For that purpose we determined the structures, band frequencies, and intensities of neutral and positively ionized naphthalene. The calculated frequencies and intensities allowed an assignment of the most important bands appearing in the newly reported experimental spectrum of the positive ion. Agreement with the experimental spectrum is satisfactory enough to take into consideration the unexpected and important result that ionization significantly affects the intensities of most vibrations. A possible consequence on the interpretation of the IR interstellar emission, generally supposed to originate from polycyclic aromatic hydrocarbons (PAHs), is briefly presented.

Calculations concerning the reaction C + H3+ --> CH(+) + H2.

The ion-molecule reaction C + H3+ --> CH(+) + H2 has not been studied in the laboratory but is thought to be important in the gas phase synthesis of organic molecules in dense interstellar clouds. We have studied this reaction theoretically by performing quantum chemical ab initio calculations on the potential surface. We find that there is no activation barrier to the reaction and that it proceeds smoothly to the first excited electronic state of CH+. The rate coefficient as a function of temperature can then be estimated using the proper long-range potentials. The rate coefficient at 10 K is calculated to be 2.9 x 10(-9) cm3 s-1.

Calculations on the rate of the ion-molecule reaction between NH3+ and H2.

The rate coefficient for the ion-molecule reaction NH3(+) + H2 --> NH4(+) + H has been calculated as a function of temperature with the use of the statistical phase space approach. The potential surface and reaction complex and transition state parameters used in the calculation have been taken from ab initio quantum chemical calculations. The calculated rate coefficient has been found to mimic the unusual temperature dependence measured in the laboratory, in which the rate coefficient decreases with decreasing temperature until 50-100 K and then increases at still lower temperatures. Quantitative agreement between experimental and theoretical rate coefficients is satisfactory given the uncertainties in the ab initio results and in the dynamics calculations. The rate coefficient for the unusual three-body process NH3(+) + H2 + He --> NH4(+) + H + He has also been calculated as a function of temperature and the result found to agree well with a previous laboratory determination.

Ab initio study of C + H3+ reactions.

The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction.

Calculations of H2O microwave line broadening in collisions with He atoms: sensitivity to potential energy surfaces.

Broadening parameters for three microwave lines of water at 22.2, 183.3, and 380.2 GHz, in a bath of helium atoms, are calculated using accurate molecular scattering S matrices obtained from two theoretical potentials presented by Palma et al., J. Chem. Phys. 89, 1401 (1988). For the 22 GHz line results are in substantial agreement with values presented in that work, indicating the accuracy of approximate methods used there. The present work improves the potential energy surfaces, computed from perturbation theory (MP4) and variational interacting correlated fragments (ICF1) wave functions, by correcting them for basis set superposition error (BSSE), and recomputes the line broadening using a different procedure for fitting computed energy points. In addition, the entire set of calculations are repeated with a quite different basis set for orbital expansion to establish the reliability of the potential energy surface. We show that adjustments for superposition error are essential, and that broadening cross sections computed from the new surfaces are changed 10%-30% from the old, significantly improving agreement with experiment. The MP4 BSSE adjusted surface appears to be the most accurate, giving room temperature broadenings of 8.9, 11.8, and 10.0 angstroms2 compared with experimental determinations of 12.2 +/- 1.2, 11.9, and 11.2 angstroms2 for the 22, 183, and 380 GHz lines, respectively. Thus, computed line to line variation is larger than observed. The ICF1 BSSE adjusted results for pressure broadening cross section parallel those from the MP4 BSSE calculations but are about 10% smaller. We believe our computed results are stable with respect to basis set for orbital expansion and that the scattering calculations are accurate. Any theoretical inadequacy has been pinpointed to too few points on the potential energy surface resulting in an inadequate description of the angle dependence. It is not clear whether the present discrepancy between computation and experiment stems from this or from errors in the experimental values, although we show some indication that additional information on the surface might decrease the computed broadenings, worsening agreement with experiment.

Ab initio determination of mode coupling in HSSH: the torsional splitting in the first excited S-S stretching state.

A mechanism for the enhanced splitting detected in the millimeter-wave rotational spectra of the first excited S-S stretching state of HSSH (disulfane) has been studied. The mechanism, which involves a potential coupling between the first excited S-S stretching state and excited torsional states, has been investigated in part by the use of ab initio theory. Based on an ab initio potential surface, coupling matrix elements have been calculated, and the amount of splitting has then been estimated by second-order perturbation theory. The result, while not in quantitative agreement with the measured splitting, lends plausibility to the assumed mechanism.

A priori predictions of the rotational constants for HC13N, HC15N, C5O.

Ab initio molecular orbital theory is used to estimate the rotational constant for several carbon-chain molecules that are candidates for discovery in interstellar space. These estimated rotational constants can be used in laboratory or astronomical searches for the molecules. The rotational constant for HC13N is estimated to be 0.1073 +/- 0.0002 GHz and its dipole moment 5.4 D. The rotational constant for HC15N is estimated to be 0.0724 GHz, with a somewhat larger uncertainty. The rotational constant of C5O is estimated to be 1.360 +/- 2% GHz and its dipole moment 4.4. D.

Can interstellar H2S be formed via gas-phase reactions? Calculations concerning the rates of the ternary and radiative association reactions between HS+ and H2.

Based on laboratory work involving the ternary association reaction of HS+ and H2 at 80 K, we have estimated the rate of the analogous radiative association reaction under interstellar conditions. Both the ternary and radiative association reactions appear to occur via a mechanism in which the electronic spin of the H3S+ complex changes before the complex is stabilized. Although this spin change is of low probability, it leads to a radiative association rate coefficient at 80 K of 7 x 10(-16) cm3 s-1 if radiative stabilization occurs at a rate of 10(3) s-1. This value of the radiative association rate coefficient at 80 K is large enough to lead to the observed abundance of H2S in the ambient ridge source in Orion.

Collisional excitation of interstellar water.

Rates for rotational excitation of water molecules in collisions with He atoms have been obtained from a new, accurate theoretical interaction potential. Rates among the lowest 40 ortho levels are given for kinetic temperatures to 1400 K and among the lowest 29 para levels for kinetic temperatures to 800 K.

Intermolecular potential for thermal H2O-He collisions.

Theoretical potentials for rotational excitation of H2O by He were constructed via several methods, all of which start with a large basis set SCF interaction. The semiempirical Hartree-Fock with damped dispersion (HFD) model adds a damped long-range attraction with parameters adjusted to fit experimental total differential cross sections. Purely ab initio potentials add correlation energies obtained via perturbation theory (MP2 and MP4) or a variational method (ICF1). Scattering calculations were performed on all surfaces to compare with available beam scattering and pressure broadening data and to assess sensitivity of state-to-state rates to uncertainties in the potential. From comparison with the limited experimental data, the ICF1 surface appears to be marginally better than the MP4 surface. Thermal rates calculated from this surface should be accurate to better than 50%, at least for the larger, more important rates.

Structural isomers of C2N+: a selected-ion flow tube study.

Reactivities of the structural isomers CCN+ and CNC+ were examined in a selected-ion flow tube at 300 +/- 5 K. The less reactive CNC+ isomer was identified as the product of the reactions of C(+) + HCN and C(+) + C2N2; in these reactions only CNC+ can be produced because of energy constraints. Rate coefficients and branching ratios are reported for the reactions of each isomer with H2, CH4, NH3, H2O, C2H2, HCN, N2, O2, N2O, and CO2. Ab initio calculations are presented for CCN+ and CNC+; a saddle point for the reaction CCN+ --> CNC+ is calculated to be 195 kJ mol-1 above the CNC+. The results provide evidence that the more reactive CCN+ isomer is unlikely to be present in measurable densities in interstellar clouds.

The sensitivity of gas-phase models of dense interstellar clouds to changes in dissociative recombination branching ratios.

The approach of Bates to the determination of neutral product branching ratios in ion-electron dissociative recombination reactions has been utilised in conjunction with quantum chemical techniques to redetermine branching ratios for a wide variety of important reactions of this class in dense interstellar clouds. The branching ratios have then been used in a pseudo time-dependent model calculation of the gas phase chemistry of a dark cloud resembling TMC-1 and the results compared with an analogous model containing previously used branching ratios. In general, the changes in branching ratios lead to stronger effects on calculated molecular abundances at steady state than at earlier times and often lead to reductions in the calculated abundances of complex molecules. However, at the so-called "early time" when complex molecule synthesis is most efficient, the abundances of complex molecules are hardly affected by the newly used branching ratios.

The C4H7+ cation. A theoretical investigation.

The potential energy surface of the C4H7+ cation has been investigated with ab initio quantum chemical theory. Extended basis set calculations, including electronic correlation, show that cyclobutyl and cyclopropylcarbinyl cation are equally stable isomers. The saddle point connecting these isomers lies 0.6 kcal/mol above the minima. The global C4H7+ minimum corresponds to the 1-methylallyl cation, which is 9.0 kcal/mol more stable than the cyclobutyl and the cyclopropylcarbinyl cation and 9.5 kcal/mol below the 2-methylallyl cation. These results are in excellent agreement with experimental data.

A detailed investigation of proposed gas-phase syntheses of ammonia in dense interstellar clouds.

The initial reactions in two proposed gas-phase synthesis of interstellar ammonia have been studied in detail. The rate of the slightly endothermic reaction N+(H2) --> NH+(H) under interstellar conditions has been reinvestigated under thermal and nonthermal (translational excitation) conditions based on low-temperature laboratory data. In the thermal case, the importance or lack of importance of this reaction in synthesizing ammonia is determined by how the existing laboratory data at low temperature are interpreted. In particular, it is unclear to what degree the greater rotational energy of laboratory H2 as compared with that of interstellar H2 affects the rate of reaction. In the nonthermal case, whether or not this reaction is important in synthesizing ammonia depends, in addition, upon which of two experimental investigations involving this reaction at low temperature is correct. The exothermic reaction N(H3+) --> NH2+(H) has been studied via ab initio quantum chemical methods and found to possess a large activation energy barrier. Consequently, this latter reaction does not take place appreciably in interstellar clouds and cannot be used to synthesize ammonia.

Collisional excitation of interstellar cyclopropenylidene.

Theoretical rotational excitation rates were computed for C3H2 in collisions with He atoms at temperatures from 30 to 120 K. The intermolecular forces were obtained from accurate self-consistent field and perturbation theory calculations, and collision dynamics were treated within the infinite-order sudden approximation. The accuracy of the latter was examined by comparing with the more exact coupled states approximation.

Ion-molecule calculation of the abundance ratio of CCD to CCH in dense interstellar clouds.

Laboratory measurements and calculations have been performed to determine the abundance ratio of the deuterated ethynyl radical (CCD) to the normal radical (CCH) which can be achieved in dense interstellar clouds via isotopic fractionation in the C2H2+ (HD) = C2HD+ (H2) system of reactions. According to this limited treatment, the CCD/CCH abundance ratio which can be attained is in the range 0.02-0.03 for the Orion molecular cloud and 0.01-0.02 for TMC-1. These ranges of numbers are in reasonable agreement with the observed values in Orion and TMC-1. However, the analysis of the CCD/CCH abundance ratio is complicated via the presence of competing fractionation mechanisms, especially in the low-temperature source TMC-1.

A high-precision ab initio determination of the equilibrium geometry and force field of HOC+.

Ab initio molecular orbital theory is used to determine if the molecular ion HOC+ is linear (as are the isoelectronic species HCN, HNC, HCO+, etc.), or if it is quasilinear. Near the Hartree-Fock limit the molecule is either linear, or very close to linear. Electron correlation favors the linear geometry, leading to the unequivocal prediction of a linear molecule. Detailed comparisons between HOC+ and isoelectronic HNC show an apparent lack of convergence in the bending potential for the former which is remedied by the addition of f functions to the basis set. The HOC+ potential energy surface is computed in the bending and bend-stretch coordinates and fit to an analytical function. Use of this function to compute the rotation-vibration energies results in improved agreement with experiment relative to previous potentials by nearly two orders of magnitude, as documented in the accompanying paper.

Is N-protonated hydrogen isocyanide, H2NC+, an observable interstellar species?

Ab initio molecular orbital theory is used to examine the singlet and triplet potential energy surfaces for the CH2N+ system. The results confirm those of earlier studies which suggested that the singlet H2NC+ isomer could be formed via the corresponding triplet isomer. Also, it is shown that the reaction HCN+ + H2 might lead to this metastable isomer without invoking the triplet species. The best test of the hypothesis that this molecule can be formed by gas phase, ion molecule reactions and may be an important precursor in the interstellar synthesis of HCN and HNC is to search for it in space. To this end, theoretical predictions are made of its rotational frequencies and its vibrational frequencies and intensities to serve as a guide to laboratory spectroscopists and radioastronomers.