A global potential energy surface is reported for the ground electronic state of HSO2 by using the double many-body expansion (DMBE) method. It employs realistic DMBE functions previously reported from accurate ab initio calculations (in some cases, fine tuned to spectroscopic data) for the triatomic fragments, and four-body energy terms that were modelled by fitting novel ab initio FVCAS/AVTZ calculations for the tetratomic system. In some cases, FVCAS/AVDZ energies have been employed after being scaled to FVCAS/AVTZ ones. To assess the role of the dynamical correlation, exploratory single-point Rayleigh-Schrödinger perturbation calculations have also been conducted at one stationary point. All reported calculations are compared with previous ab initio results for the title system. The potential energy surface predicts HOSO to be the most stable configuration, in good agreement with other theoretical data available in the literature. In turn, the HSO2 isomer with H bonded to S is described as a local minimum, which is stable with respect to the H + SO2 dissociation asymptote.

GEMS is an IRAM 30m Large Program whose aim is determining the elemental depletions and the ionization fraction in a set of prototypical star-forming regions. This paper presents the first results from the prototypical dark cloud TMC 1. Extensive millimeter observations have been carried out with the IRAM 30m telescope (3 mm and 2 mm) and the 40m Yebes telescope (1.3 cm and 7 mm) to determine the fractional abundances of CO, HCO+, HCN, CS, SO, HCS+, and N2H+ in three cuts which intersect the dense filament at the well-known positions TMC 1-CP, TMC 1-NH3, and TMC 1-C, covering a visual extinction range from AV ~ 3 to ~20 mag. Two phases with differentiated chemistry can be distinguished: i) the translucent envelope with molecular hydrogen densities of 1–5×103 cm−3; and ii) the dense phase, located at AV > 10 mag, with molecular hydrogen densities >104 cm−3. Observations and modeling show that the gas phase abundances of C and O progressively decrease along the C+/C/CO transition zone (AV ~ 3 mag) where C/H ~ 8×10−5 and C/O~0.8–1, until the beginning of the dense phase at AV ~ 10 mag. This is consistent with the grain temperatures being below the CO evaporation temperature in this region. In the case of sulfur, a strong depletion should occur before the translucent phase where we estimate a S/H ~ (0.4 - 2.2) ×10−6, an abundance ~7-40 times lower than the solar value. A second strong depletion must be present during the formation of the thick icy mantles to achieve the values of S/H measured in the dense cold cores (S/H ~8×10−8). Based on our chemical modeling, we constrain the value of ζH2 to ~ (0.5 - 1.8) ×10−16 s−1 in the translucent cloud.

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The importance of the HSO(2) system in atmospheric and combustion chemistry has motivated several works dedicated to the study of associated structures and chemical reactions. Nevertheless controversy still exists in connection with the reaction SH + O(2)→ H + SO(2) and also related to the role of the HSOO isomers in the potential energy surface (PES). Here we report high-level ab initio calculation for the electronic ground state of the HSO(2) system. Energetic, geometric, and frequency properties for the major stationary states of the PES are reported at the same level of calculations: CASPT2/aug-cc-pV(T+d)Z. This study introduces three new stationary points (two saddle points and one minimum). These structures allow the connection of the skewed HSOO(s) and the HSO(2) minima defining new reaction paths for SH + O(2) → H + SO(2) and SH + O(2) → OH + SO. In addition, the location of the HSOO isomers in the reaction pathways have been clarified.

Oscillatory and stationary convective patterns in a reaction driven gravity current J. Chem. Phys. 135, 204501 (2011) Cross sections and rate constants for OH + H2 reaction on three different potential energy surfaces for rovibrationally excited reagents J. Chem. Phys. 135, 194302 (2011) Effects of solvation shells and cluster size on the reaction of aluminum clusters with water AIP Advances 1, 042149 (2011) Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4He + H2 4HeH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass J. Chem. Phys. 135, 184310 (2011) State-to-state quantum dynamics of the N(4S) + OH(X2) H(2S) + NO(X2) reaction J. Chem. Phys. 135, 164312 (2011) Additional information on J. Chem. Phys. A full dimensional quasiclassical trajectory study of the OH+ SO reaction is presented with the aim of investigating the role of the reactants rotational energy in the reactivity. Different energetic combinations with one and both reactants rotationally excited are studied. A passive method is used to correct zero-point-energy leakage in the classical calculations. The reactive cross sections, for each combination, are calculated and fitted to a capturelike model combined with a factor accounting for recrossing effects. Reactivity decreases as rotational energy is increased in any of both reactants. This fact provides a theoretical support for the experimental dependence of the rate constant on temperature.