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From left to right and top to bottom, the five Ge ₂ H ₂ ⁺ structures are shown: trans , monobridged, butterfly, germylidene, and linear.

Criegee intermediates, formed from the ozonolysis of alkenes, are known to have a role in atmospheric chemistry, including the modulation of the oxidizing capacity of the troposphere. Although studies have been conducted since their discovery, the synthesis of these species in the laboratory has ushered in a new wave of investigations of these structures, both theoretically and experimentally. In some of these theoretical studies, high-order corrections for correlation energy are included to account for the mid multi-reference character found in these systems. Many of these studies include a focus on kinetics; therefore, the calculated energies should be accurate (<1 kcal/molmore » in error). In this research, we compute the enthalpies of formation for a small set of Criegee intermediates, including higher-order coupled cluster corrections for correlation energy up to coupled cluster with perturbative quintuple excitations. The enthalpies of formation for formaldehyde oxide, anti-acetaldehyde oxide, syn-acetaldehyde oxide, and acetone oxide are presented at 0 K as 26.5, 15.6, 12.2, and 0.1 kcal mol−1, respectively. Additionally, we do not recommend the coupled cluster with perturbative quadruple excitations [CCSDT(Q)] energy correction, as it is approximately twice as large as that of the coupled cluster with full quadruple excitations (CCSDTQ). Half of the CCSDT(Q) energy correction may be included as a reliable, cost-effective estimation of CCSDTQ energies for Criegee intermediates.« less

Butyl radicals (n-, s-, i-, and tert-butyl) are formed from the pyrolysis of stable precursors (1-pentyl nitrite, 2-methyl-1-butyl nitrite, isopentyl nitrite, and azo-tert-butane, respectively). The radicals are doped into a beam of liquid helium droplets and probed with infrared action spectroscopy from 2700 to 3125 cm^-1, allowing for a low temperature measurement of the CH stretching region. The presence of anharmonic resonance polyads in the 2800–3000 cm^-1 region complicates its interpretation. To facilitate spectral assignment, the anharmonic resonances are modeled with two model Hamiltonian approaches that explicitly couple CH stretch fundamentals to HCH bend overtones and combinations: a VPT2+K normalmore » mode model based on coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] quartic force fields and a semi-empirical local mode model. Both of these computational methods provide generally good agreement with the experimental spectra.« less

Four different reaction pathways are initially located for the reaction of Cl atom plus water trimer Cl + (H₂O)₃ → HCl + (H₂O)₂OH using a standard DFT method. As found for the analogous fluorine reaction, the geometrical and energetic results for the four chlorine pathways are closely related. However, the energetics for the Cl reaction are very different from those for fluorine. Here in this paper, we investigate the lowest-energy chlorine pathway using the “gold standard” CCSD(T) method in conjunction with correlation-consistent basis sets up to cc-pVQZ. Structurally, the stationary points for the water trimer reaction Cl + (H₂O)₃ maymore » be compared to those for the water monomer reaction Cl + H₂O and water dimer reaction Cl + (H₂O)₂. Based on the CCSD(T) energies, the title reaction is endothermic by 19.3 kcal mol^-1, with a classical barrier height of 16.7 kcal mol^-1 between the reactants and the exit complex. There is no barrier for the reverse reaction. The Cl^…(H₂O)₃ entrance complex lies 5.3 kcal mol^-1 below the separated reactants. The HCl^…(H₂O)₂OH exit complex is bound by 8.6 kcal mol^-1 relative to the separated products. The Cl + (H₂O)₃ reaction is somewhat similar to the analogous Cl + (H₂O)₂ reaction, but qualitatively different from the Cl + H₂O reaction. It is reasonable to expect that the reactions between the chlorine atom and larger water clusters may be similar to the Cl + (H₂O)₃ reaction. The potential energy profile for the Cl + (H₂O)₃ reaction is radically different from that for the valence isoelectronic F + (H₂O)₃ system, which may be related to the different bond energies between HCl and HF.« less

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Sulfurous acid (H₂SO₃) is an infamously elusive molecule. Although some theoretical papers have supposed possible roles for it in more complicated systems, it has yet to be experimentally observed. To aid experiment in detecting this molecule, we have examined the H₂O + SO₂ potential energy surface at the CCSDT(Q)/CBS//CCSD(T)-F12b/cc-pVTZ-F12b level of theory to resolve standing discrepancies in previous reports and predict the gas-phase vibrational spectrum for H₂SO₃. We find that sulfurous acid has two potentially detectable rotamers, separated by 1.1 kcal mol^-1 ΔH-_0K with a torsional barrier of 1.6 kcal mol^-1. The sulfonic acid isomer is only 6.9 kcal mol^-1more » above the lowest enthalpy sulfurous acid rotamer, but the barrier to form it is 57.2 kcal mol^-1. Error in previous reports can be attributed to misidentified stationary points, the use of density functionals that perform poorly for this system, and, most importantly, the basis set sensitivity of sulfur. Using VPT2+K, we determine that the intense S=O stretch fundamental of each species is separated from other intense peaks by at least 25 cm^-1, providing a target for identification by infrared spectroscopy. Published under license by AIP Publishing.« less

Three constitutional isomers of both Ca₂H₂ and Ca₂H₄ have been characterized with molecular electronic structure theory. Correlation methods as complete as CCSDT(Q) and basis sets as large as cc-pwCV5Z have been used to converge the relative energies within chemical accuracy (≤1 kcal mol^-1). Anharmonic vibrational frequencies were computed using second-order vibrational perturbation theory employing CCSD(T)/cc-pwCVTZ cubic and quartic force-fields and a CCSD(T)/cc-pwCVQZ quadratic force field. The monobridged [Ca(μ₂-H)CaH] and dibridged [Ca(μ₂-H)₂Ca] isomers of Ca₂H₂ were predicted to lie 6.5 and 12.9 kcal mol^-1 below the energy of the classical HCaCaH linear isomer, respectively. Despite the energetic favorability of the bridgedmore » Ca₂H₂ isomers, we conclude (surprisingly) that only the higher energy linear structure has been observed in the laboratory. At 0 K, the tribridged [Ca(μ₂-H)₃CaH] isomer of Ca₂H₄ is predicted to be enthalpically favored by 0.9 kcal mol^-1 in comparison to the enthalpy of the dibridged [HCa(μ₂-H)₂CaH] structure. Comparison of experiment with our computed frequencies suggests that the observed vibrational features arise from both the dibridged and the tribridged Ca₂H₄ structures.« less

Vinoxy radicals are involved in numerous atmospheric and combustion mechanisms. High-level theoretical methods have recently shed new light on the reaction of the unsubstituted vinoxy radical with O₂. The reactions of 1-methylvinoxy radical and 2-methylvinoxy radical with molecular oxygen have experimental high pressure limiting rate constants, k_∞, 5–7 times higher than that of the vinoxy plus O₂ reaction. In this work, high-level ab initio quantum chemical computations are applied to the 2-methylvinoxy radical plus O₂ system, namely, the formation and isomerization of the 1-oxo-2-propylperoxy radical, the immediate product of O₂ addition to the 2-methylvinoxy radical. Multireference methods were applied tomore » the entrance channel. No barrier to O₂ addition could be located, and more sophisticated treatment of dynamic electron correlation shows that the principal difference between O₂ addition to the vinoxy and 2-methylvinoxy radicals is a larger steric factor for 2-methylvinoxy + O₂. This is attributed to the favorable interaction between the incoming O₂ molecule and the methyl group of the 2-methylvinoxy radical. Via the focal point approach, energetics for this reaction were determined, in most cases, to chemical accuracy. The coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] correlation energy and Hartree–Fock energies were independently extrapolated to the complete basis set limit. A correction for the effect of higher excitations was computed at the CCSDT(Q)/6-31G level. Corrections for the frozen-core approximation, the Born–Oppenheimer approximation, the nonrelativistic approximation, and the zero-point vibrational energy were included. From the 1-oxo-2-propylperoxy radical, dissociation to reactants is competitive with the lowest energy isomerization pathway. The lowest energy isomerization pathway ultimately forms acetaldehyde, CO, and ·OH as the final products.« less