Pathways for the OH + Cl<inf>2</inf> → HOCl + Cl and HOCl + Cl → HCl + ClO Reactions

High level coupled-cluster theory, with spin-orbit coupling evaluated via the Breit-Pauli operator in the interacting-states approach, is used to investigate the OH radical reaction with Cl2 and the subsequent reaction HOCl + Cl. The entrance complex, transition state, and exit complex for both reactions have been determined using the CCSD(T) method with correlation consistent basis sets up to cc-pV6Z. Also reported are CCSDT computations. The OH + Cl2 reaction is predicted to be endothermic by 2.2 kcal/mol, compared to the best experiments, 2.0 kcal/mol. The above theoretical results include zero-point vibrational energy corrections and spin-orbit contributions. The activation energy (Ea) of the OH + Cl2 reaction predicted here, 2.3 kcal/mol, could be as much as 1 kcal/mol too high, but it falls among the four experimental Ea values, which span the range 1.1-2.5 kcal/mol. The exothermicity of the second reaction HOCl + Cl → HCl + ClO is 8.4 kcal/mol, compared to experiment 8.7 kcal/mol. The activation energy for latter reaction is unknown experimentally, but predicted here to be large, 11.5 kcal/mol. There are currently no experiments relevant to the theoretical entrance and exit complexes predicted here. © 2015 American Chemical Society

Heptacarbonyldiosmium and Hexacarbonyldiosmium: Two Highly Unsaturated Binuclear Osmium Carbonyls

A total of nine singlet structures for Os2(CO)7 and 15 structures (nine singlet and six triplet) for Os2(CO)6 have been found by density functional theory thereby indicating very complicated energy surfaces. The global minimum for Os2(CO)7 is a doubly carbonyl bridged structure Os2(CO)5(μ-CO)2 with an Os=Os distance of 2.67 Å suggesting a formal double bond and hence a 16-electron rather than an 18-electron configuration for one of the osmium atoms. However, at only slightly higher energy (3.2 kcal mol−1) lies an unbridged Os2(CO)7 structure with a shorter Os≡Os distance of 2.54 Å, corresponding to a formal triple bond and an 18-electron configuration for each osmium atom. The global minimum for Os2(CO)6 can be derived from that of Os2(CO)7 by removal of a carbonyl group while retaining the Os=Os double bond and the two bridging carbonyl groups. Slightly higher energy Os2(CO)6 structures at ≈3 kcal mol−1 or more above the global minimum have short Os-Os quadrupole bond distances around 2.4 Å, consistent with the formal quadruple bonds necessary to give both osmium atoms the favored 18-electron configuration. None of the 24 structures for Os2(CO)7 and Os2(CO)6 found in this work has a four-electron donor η2-μ-CO bridging carbonyl group

Coupled Cluster Externally Corrected by Adaptive Configuration Interaction

An externally corrected coupled cluster (CC) method, where an adaptive configuration interaction (ACI) wave function provides the external cluster amplitudes, named ACI-CC, is presented. By exploiting the connection between configuration interaction and coupled cluster through cluster analysis, the higher-order T3 and T4 terms obtained from ACI are used to augment the T1 and T2 amplitude equations from traditional coupled cluster. These higher-order contributions are kept frozen during the coupled cluster iterations and do not contribute to an increased cost with respect to CCSD. We have benchmarked this method on three closed-shell systems: beryllium dimer, carbonyl oxide, and cyclobutadiene, with good results compared to other corrected coupled cluster methods. In all cases, the inclusion of these external corrections improved upon the "gold standard" CCSD(T) results, indicating that ACI-CCSD(T) can be used to assess strong correlation effects in a system and as an inexpensive starting point for more complex external corrections

Characterization of Singlet Ground and Low-Lying Electronic Excited States of Phosphaethyne and Isophosphaethyne

The singlet ground _X˜ 1_+_ and excited _1_− , 1__ states of HCP and HPC have been systematically investigated using ab initio molecular electronic structure theory. For the ground state, geometries of the two linear stationary points have been optimized and physical properties have been predicted utilizing restricted self-consistent field theory, coupled cluster theory with single and double excitations _CCSD_, CCSD with perturbative triple corrections _CCSD_T__, and CCSD with partial iterative triple excitations _CCSDT-3 and CC3_. Physical properties computed for the global minimum _X˜ 1_+HCP_ include harmonic vibrational frequencies with the cc-pV5Z CCSD_T_ method of _1=3344 cm−1, _2=689 cm−1, and _3=1298 cm−1. Linear HPC, a stationary point of Hessian index 2, is predicted to lie 75.2 kcal mol−1 above the global minimum HCP. The dissociation energy D0_HCP_X˜ 1_+_→H_2S_+CP_X 2_+__ of HCP is predicted to be 119.0 kcal mol−1, which is very close to the experimental lower limit of 119.1 kcal mol−1. Eight singlet excited states were examined and their physical properties were determined employing three equation-of-motion coupled cluster methods _EOM-CCSD, EOM-CCSDT-3, and EOM-CC3_. Four stationary points were located on the lowest-lying excited state potential energy surface, 1_− →1A_, with excitation energies Te of 101.4 kcal mol−1_1A_ HCP_, 104.6 kcal mol−1_1_− HCP_, 122.3 kcal mol−1_1A_ HPC_, and 171.6 kcal mol−1_1_− HPC_ at the cc-pVQZ EOM-CCSDT-3 level of theory. The physical properties of the 1A_ state with a predicted bond angle of 129.5° compare well with the experimentally reported first singlet state _A˜ 1A__. The excitation energy predicted for this excitation is T0=99.4 kcal mol−1_34 800 cm−1 , 4.31 eV_, in essentially perfect agreement with the experimental value of T0=99.3 kcal mol−1_34 746 cm−1 ,4.308 eV_. For the second lowest-lying excited singlet surface, 1_→1A_, four stationary points were found with Te values of 111.2 kcal mol−1 _21A_ HCP_, 112.4 kcal mol−1 _1_ HPC_, 125.6 kcal mol−1_2 1A_ HCP_, and 177.8 kcal mol−1_1_ HPC_. The predicted CP bond length and frequencies of the 2 1A_ state with a bond angle of 89.8° _1.707 Å, 666 and 979 cm−1_ compare reasonably well with those for the experimentally reported C ˜ 1A_ state _1.69 Å, 615 and 969 cm−1_. However, the excitation energy and bond angle do not agree well: theoretical values of 108.7 kcal mol−1 and 89.8° versus experimental values of 115.1 kcal mol−1 and 113°

Radiative decay lifetimes of CH^-₂

Recently the presence and radiative decay of vibrationally excited CH - 2, generated in a hot cathode discharge of methane, was established by measuring the time dependent photodetachment from excited states of CH - 2 as it radiatively relaxed in a high vacuum ion trap. The time dependence of the photodetachment was found to be consistent with an electron affinity of 5250 cm^−1 (0.65 eV) for ground state X-tilde 3B1 methylene. The radiative decay lifetimes of the first three excited bending vibrations of CH - 2 were also tentatively assigned. Here, we report a more refined analysis of the experimental data along with theoretical ab initio determinations of the radiative decay lifetimes of the first four excited bending vibrational levels of CH - 2. There is some discrepancy between the ab initio values (431, 207, 118, and 68 ms for the v2=1, 2, 3, and 4 levels respectively) and the experimental values (525, 70, and 14 ms for v2=1, 2, and 3 respectively) for v2=2 and 3. Possible reasons for this discrepancy are discussed but none of the alternatives are entirely satisfactory

Orbital Elements and Stellar Parameters of the Active Binary UX Arietis

This is the final version of the article. Available from American Astronomical Society via the DOI in this record.Stellar activity observed as large surface spots, radio flares, or emission lines is often found in binary systems. UX Arietis exhibits these signs of activity, originating on the K0 subgiant primary component. Our aim is to resolve the binary, measure the orbital motion, and provide accurate stellar parameters such as masses and luminosities to aid in the interpretation of the observed phenomena. Using the CHARA six-telescope optical long-baseline array on Mount Wilson, California, we obtained amplitudes and phases of the interferometric visibility on baselines up to 330 m in length, resolving the two components of the binary. We reanalyzed archival Center for Astrophysics spectra to disentangle the binary component spectra and the spectrum of the third component, which was resolved by speckle interferometry. We also obtained new spectra with the Nordic Optical Telescope, and we present new photometric data that we use to model stellar surface spot locations. Both interferometric visibilities and spectroscopic radial velocities are modeled with a spotted primary stellar surface using the Wilson–Devinney code. We fit the orbital elements to the apparent orbit and radial velocity data to derive the distance (52.1 ± 0.8 pc) and stellar masses (MP = 1.30 0.06 M, MS = 1.14 0.06 M). The radius of the primary can be determined to be RP = 5.6 0.1 R and that of the secondary to be RS = 1.6 0.2 R. The equivalent spot coverage of the primary component was found to be 62% with an effective temperature 20% below that of the unspotted surface.We thank Robert Wilson (University of Florida) for providing a custom version of his code to compute images of spotted stellar surfaces and for his help with using it. This work is based upon observations obtained with the Georgia State University (GSU) Center for High Angular Resolution Astronomy (CHARA) array at Mount Wilson Observatory. The CHARA array is supported by the National Science Foundation under grant numbers AST-1211929 and AST-1411654. Institutional support has been provided by the GSU College of Arts and Sciences and the GSU Office of the Vice President for Research and Economic Development. The MIRC instrument at the CHARA array was funded by the University of Michigan. F.B., R.R., and J.D.M. acknowledge support from NSF-AST 1210972 and 1108963. G.T. acknowledges partial support from NSF grant AST-1509375. S.K. acknowledges support from an STFC Rutherford Fellowship (ST/J004030/1) and ERC Starting Grant (grant agreement no. 639889). This work is also based on observations made with the Nordic Optical Telescope (NOT), operated by the Nordic Optical Telescope Scientific Association at the Observatorio del Roque de los Muchachos, La Palma, Spain, of the Instituto de Astrofisica de Canarias. This research has made use of the SIMBAD database, operated at the CDS, Strasbourg, France. This research has made use of the Jean-Marie Mariotti Center SearchCal service13 codeveloped by FIZEAU and LAOG/IPAG and of the CDS astronomical databases SIMBAD and VIZIER.14 This research has made use of the Washington Double Star Catalog, maintained at the U.S. Naval Observatory. We thank Nicholas Elias II for discussions. We thank Dimitri Pourbaix for maintaining and providing access to the SB9 database of RV measurements of spectroscopic binaries

Contemporaneous Imaging Comparisons of the Spotted Giant σ Geminorum Using Interferometric, Spectroscopic, and Photometric Data

Nearby active stars with relatively rapid rotation and large starspot structures offer the opportunity to compare interferometric, spectroscopic, and photometric imaging techniques. In this paper, we image a spotted star with three different methods for the first time. The giant primary star of the RS Canum Venaticorum binary sigma. Geminorum (sigma Gem) was imaged for two epochs of interferometric, high-resolution spectroscopic, and photometric observations. The light curves from the reconstructions show good agreement with the observed light curves, supported by the longitudinally consistent spot features on the different maps. However, there is strong disagreement in the spot latitudes across the methods