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1. Thermochemistry and mechanisms of the Pt ⁺ + SO ₂ reaction from guided ion beam tandem mass spectrometry and theory

   https://doi.org/10.1063/5.0091510  

   Armentrout, P. B. ( May 2022 , The Journal of Chemical Physics)

   The kinetic energy dependences of the reactions of Pt + ( 2 D 5/2 ) with SO 2 were studied using a guided ion beam tandem mass spectrometer and theory. The observed cationic products are PtO + and PtSO + , with small amounts of PtS + , all formed in endothermic reactions. Modeling the kinetic energy dependent product cross sections allows determination of the product bond dissociation energies (BDEs): D 0 (Pt + –O) = 3.14 ± 0.11 eV, D 0 (Pt + –S) = 3.68 ± 0.31 eV, and D 0 (Pt + –SO) = 3.03 ± 0.12 eV. The oxide BDE agrees well with more precise literature values, whereas the latter two results are the first such measurements. Quantum mechanical calculations were performed for PtO + , PtS + , PtO 2 + , and PtSO + at the B3LYP and coupled-cluster with single, double, and perturbative triple [CCSD(T)] levels of theory using the def2-XZVPPD (X = T, Q) and aug-cc-pVXZ (X = T, Q, 5) basis sets and complete basis set extrapolations. These theoretical BDEs agree well with the experimental values. After including empirical spin–orbit corrections, the product ground states are determined as PtO + ( 4 Σ 3/2more »), PtS + ( 4 Σ 3/2 ), PtO 2 + ( 2 Σ g + ), and PtSO + ( 2 A′). Potential energy profiles including intermediates and transition states for each reaction were also calculated at the B3LYP/def2-TZVPPD level. Periodic trends in the thermochemistry of the group 9 metal chalcogenide cations are compared, and the formation of PtO + from the Pt + + SO 2 reaction is compared with those from the Pt + + O 2 , CO 2 , CO, and NO reactions.« less
2. A thermo-photo hybrid process for steam reforming of methane: highly efficient visible light photocatalysis

   https://doi.org/10.1039/c9cc04193a  

   Han, Bing ; Wei, Wei ; Li, Meijia ; Sun, Kai ; Hu, Yun Hang ( July 2019 , Chemical Communications)

   Steam reforming of methane (SRM) is one of the most important industrial processes, which produces 95% of hydrogen used in the USA. However, SRM is an endothermic reaction, which requires a high energy input and a high reaction temperature (>800 °C) for the current process. Furthermore, its products must be subjected to a water–gas shift (WGS) process. A photocatalytic process is expected to solve the energy issue and to eliminate the necessity of WGS for SRM. However, the hydrogen yield from the current photocatalytic steam reforming of methane (PSRM) is very low (μmol h −1 g −1 level), which is far below industrial interest. This work demonstrates that a Pt/blackTiO 2 catalyst dispersed on a light-diffuse-reflection-surface is excellent for efficient visible-light PSRM. Under visible light illumination on the catalyst by filtering UV light from AM 1.5G sunlight, CH 4 and H 2 O were directly converted into H 2 and CO 2 without WGS, leading to a high H 2 yield of 185 mmol h −1 g −1 with a quantum efficiency of 60% at 500 °C. The yield is 3 orders of magnitude larger than the reported values, which can be attributed to the synergistic effect between potential andmore »kinetic energies. This opens up a new opportunity for hydrogen production from water and natural gas using solar energy.« less
3. Pressure-dependent kinetics of peroxy radicals formed in isobutanol combustion

   https://doi.org/10.1039/d0cp02872j  

   Goldman, Mark Jacob ; Yee, Nathan W. ; Kroll, Jesse H. ; Green, William H. ( September 2020 , Physical Chemistry Chemical Physics)

   Bio-derived isobutanol has been approved as a gasoline additive in the US, but our understanding of its combustion chemistry still has significant uncertainties. Detailed quantum calculations could improve model accuracy leading to better estimation of isobutanol's combustion properties and its environmental impacts. This work examines 47 molecules and 38 reactions involved in the first oxygen addition to isobutanol's three alkyl radicals located α, β, and γ to the hydroxide. Quantum calculations are mostly done at CCSD(T)-F12/cc-pVTZ-F12//B3LYP/CBSB7, with 1-D hindered rotor corrections obtained at B3LYP/6-31G(d). The resulting potential energy surfaces are the most comprehensive isobutanol peroxy networks published to date. Canonical transition state theory and a 1-D microcanonical master equation are used to derive high-pressure-limit and pressure-dependent rate coefficients, respectively. At all conditions studied, the recombination of γ-isobutanol radical with O 2 forms HO 2 + isobutanal. The recombination of β-isobutanol radical with O 2 forms a stabilized hydroperoxy alkyl radical below 400 K, water + an alkoxy radical at higher temperatures, and HO 2 + an alkene above 1200 K. The recombination of β-isobutanol radical with O 2 results in a mixture of products between 700–1100 K, forming acetone + formaldehyde + OH at lower temperatures and forming HO 2more »+ alkenes at higher temperatures. The barrier heights, high-pressure-limit rates, and pressure-dependent kinetics generally agree with the results from previous quantum chemistry calculations. Six reaction rates in this work deviate by over three orders of magnitude from kinetics in detailed models of isobutanol combustion, suggesting the rates calculated here can help improve modeling of isobutanol combustion and its environmental fate.« less
4. Atomic Transition Probabilities for Transitions of Si i and Si ii and the Silicon Abundances of Several Very Metal-poor Stars ^∗  

   https://doi.org/10.3847/1538-4365/acb642  

   Den Hartog, E. A. ; Lawler, J. E. ; Sneden, C. ; Roederer, I. U. ; Cowan, J. J. ( March 2023 , The Astrophysical Journal Supplement Series)

   We report new measurements of branching fractions for 20 UV and blue lines in the spectrum of neutral silicon (Sii) originating in the 3s²3p4s³P^o_1,2,¹P^o₁, and 3s3p³¹D^o_1,2upper levels. Transitions studied include both strong, nearly pure LS multiplets as well as very weak spin-forbidden transitions connected to these upper levels. We also report a new branching fraction measurement of the⁴P_1/2–²P^o_1/2,3/2intercombination lines in the spectrum of singly ionized silicon (Siii). The weak spin-forbidden lines of Siiand Siiiprovide a stringent test on recent theoretical calculations, to which we make comparison. The branching fractions from this study are combined with previously reported radiative lifetimes to yield transition probabilities and log(gf) values for these lines. We apply these new measurements to abundance determinations in five metal-poor stars.
5. Assessment of electronic structure methods for the determination of the ground spin states of Fe( ii ), Fe( iii ) and Fe( iv ) complexes

   https://doi.org/10.1039/C7CP01263B  

   Verma, Pragya ; Varga, Zoltan ; Klein, Johannes E. ; Cramer, Christopher J. ; Que, Lawrence ; Truhlar, Donald G. ( January 2017 , Physical Chemistry Chemical Physics)

   Our ability to understand and simulate the reactions catalyzed by iron depends strongly on our ability to predict the relative energetics of spin states. In this work, we studied the electronic structures of Fe 2+ ion, gaseous FeO and 14 iron complexes using Kohn–Sham density functional theory with particular focus on determining the ground spin state of these species as well as the magnitudes of relevant spin-state energy splittings. The 14 iron complexes investigated in this work have hexacoordinate geometries of which seven are Fe( ii ), five are Fe( iii ) and two are Fe( iv ) complexes. These are calculated using 20 exchange–correlation functionals. In particular, we use a local spin density approximation (LSDA) – GVWN5, four generalized gradient approximations (GGAs) – BLYP, PBE, OPBE and OLYP, two non-separable gradient approximations (NGAs) – GAM and N12, two meta-GGAs – M06-L and M11-L, a meta-NGA – MN15-L, five hybrid GGAs – B3LYP, B3LYP*, PBE0, B97-3 and SOGGA11-X, four hybrid meta-GGAs – M06, PW6B95, MPW1B95 and M08-SO and a hybrid meta-NGA – MN15. The density functional results are compared to reference data, which include experimental results as well as the results of diffusion Monte Carlo (DMC) calculations and ligand fieldmore »theory estimates from the literature. For the Fe 2+ ion, all functionals except M11-L correctly predict the ground spin state to be quintet. However, quantitatively, most of the functionals are not close to the experimentally determined spin-state splitting energies. For FeO all functionals predict quintet to be the ground spin state. For the 14 iron complexes, the hybrid functionals B3LYP, MPW1B95 and MN15 correctly predict the ground spin state of 13 out of 14 complexes and PW6B95 gets all the 14 complexes right. The local functionals, OPBE, OLYP and M06-L, predict the correct ground spin state for 12 out of 14 complexes. Two of the tested functionals are not recommended to be used for this type of study, in particular M08-SO and M11-L, because M08-SO systematically overstabilizes the high spin state, and M11-L systematically overstabilizes the low spin state.« less