The challenging equilibrium structure of HSSH: Another success of the rotational spectroscopy / quantum chemistry synergism

Ye, Hexu; Mendolicchio, Marco; Kruse, Holger; Puzzarini, Cristina; Biczysko, Małgorzata; Barone, Vincenzo

doi:10.1016/j.molstruc.2020.127933

Cited by 16 publications

(10 citation statements)

References 75 publications

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“…Attention has been primarily focused in extending the database with species formed by biochemically relevant elements. Specifically, in addition to propyne, 12 nitrogen- and/or oxygen-bearing molecules have been added (HNO, NH 2 OH, CH 2 NH, CH 2 NOH, CO 2 , succinic anhydride, phenol, oxazole, isoxazole, glycidol, cyclopropenone, and glycine) and the number of sulfur compounds has been increased substantially with the inclusion of sulfur dioxide, dimethyl sulfide, dimethyl sulfoxide, sulfinylmethane, hydrogen disulfide, diallyl disulfide, and diphenyl disulfide, with the last three molecules involving a sulfur–sulfur bridge. Since phosphorus is a biologically relevant element not represented in the database, efforts have been made to overcome this limit, resulting in the inclusion of the PH 3 , CH 3 CP, CH 2 PH, and HPO molecules for which an accurate SE equilibrium geometry has been worked out in the literature.…”

Section: Resultsmentioning

confidence: 99%

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Ceselin

Barone

Tasinato

2021

J. Chem. Theory Comput.

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153

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The determination of accurate equilibrium molecular structures plays a fundamental role for understanding many physical–chemical properties of molecules, ranging from the precise evaluation of the electronic structure to the analysis of the role played by dynamical and environmental effects in tuning their overall behavior. For small semi-rigid systems in the gas phase, state-of-the-art quantum chemical computations rival the most sophisticated experimental (from, for example, high-resolution spectroscopy) results. For larger molecules, more effective computational approaches must be devised. To this end, we have further enlarged the compilation of available semi-experimental (SE) equilibrium structures, now covering the most important fragments containing H, B, C, N, O, F, P, S, and Cl atoms collected in the new SE100 database. Next, comparison with geometries optimized by methods rooted in the density functional theory showed that the already remarkable results delivered by PW6B95 and, especially, rev-DSDPBEP86 functionals can be further improved by a linear regression (LR) approach. Use of template fragments (taken from the SE100 library) together with LR estimates for the missing interfragment parameters paves the route toward accurate structures of large molecules, as witnessed by the very small deviations between computed and experimental rotational constants. The whole approach has been implemented in a user-friendly tool, termed nano-LEGO, and applied to a number of demanding case studies.

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Section: Resultsmentioning

confidence: 99%

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Ceselin

Barone

Tasinato

2021

J. Chem. Theory Comput.

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153

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“…a Bond lengths in Å, angles in deg. b Semi-experimental structure from Ye et al (2020). Values in parentheses are the standard deviation (first value) and the confidence interval at a 95% confidence level (second value).…”

Section: New Model Chemistries At Workmentioning

confidence: 99%

“…It is also noteworthy that the hybrid PW6B95-D3 functional reproduces the semiexperimental structure of the complex with an accuracy that, in spite of the considerably reduced computational cost, rivals that of the B2 and rev-DSD-PBEP86 double-hybrids. In order to understand whether the quite large deviation observed for the inter-molecular S-S distance is due to an intrinsic inaccuracy for S-S bonds or to an unbalanced treatment of inter-molecular interactions, the equilibrium geometry of hydrogen disulfide, HSSH (Figure 7B), has been computed at the PW6B95-D3/julcc-pV(D+d)Z level and compared with the semi-experimental structure recently reported by Ye et al (2020). The obtained structural parameters, detailed in Table 2, show deviations of 8 and 9 mÅ for the S-S and S-H bond lengths, respectively, and of 0.3 • for the HSS angle, while the HSSH dihedral is within the uncertainty of the semi-experimental value.…”

Section: New Model Chemistries At Workmentioning

confidence: 99%

Accuracy Meets Interpretability for Computational Spectroscopy by Means of Hybrid and Double-Hybrid Functionals

et al. 2020

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Accuracy and interpretability are often seen as the devil and holy grail in computational spectroscopy and their reconciliation remains a primary research goal. In the last few decades, density functional theory has revolutionized the situation, paving the way to reliable yet effective models for medium size molecules, which could also be profitably used by non-specialists. In this contribution we will compare the results of some widely used hybrid and double hybrid functionals with the aim of defining the most suitable recipe for all the spectroscopic parameters of interest in rotational and vibrational spectroscopy, going beyond the rigid rotor/harmonic oscillator model. We will show that last-generation hybrid and double hybrid functionals in conjunction with partially augmented double-and triple-zeta basis sets can offer, in the framework of second order vibrational perturbation theory, a general, robust, and user-friendly tool with unprecedented accuracy for medium-size semi-rigid molecules.

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“…d Previous experimental centrifugal distortion constants from [ 81 ]. e Previous theoretical geometrical parameters at the HF/VnZ(Q,5,6) + fc-CCSD(T)/VnZ(q,5) + CV/CCSD(T)/CVQZ level of theory with full-T,Q corrections and DPT2 corrections from [ 82 ]. f Previous experimental rotational constants from [ 83 ].…”

Section: Figurementioning

confidence: 99%

Spectral Signatures of Hydrogen Thioperoxide (HOSH) and Hydrogen Persulfide (HSSH): Possible Molecular Sulfur Sinks in the Dense ISM

2022

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For decades, sulfur has remained underdetected in molecular form within the dense interstellar medium (ISM), and somewhere a molecular sulfur sink exists where it may be hiding. With the discovery of hydrogen peroxide (HOOH) in the ISM in 2011, a natural starting point may be found in sulfur-bearing analogs that are chemically similar to HOOH: hydrogen thioperoxide (HOSH) and hydrogen persulfide (HSSH). The present theoretical study couples the accuracy in the anharmonic fundamental vibrational frequencies from the explicitly correlated coupled cluster theory with the accurate rotational constants provided by canonical high-level coupled cluster theory to produce rovibrational spectra for use in the potential observation of HOSH and HSSH. The ν6 mode for HSSH at 886.1 cm−1 is within 0.2 cm−1 of the gas-phase experiment, and the B0 rotational constant for HSSH of 6979.5 MHz is within 9.0 MHz of the experimental benchmarks, implying that the unknown spectral features (such as the first overtones and combination bands) provided herein are similarly accurate. Notably, a previous experimentally-attributed 2ν1 mode, at 7041.8 cm−1, has been reassigned to the ν1+ν5 combination band based on the present work’s ν1+ν5 value at 7034.3 cm−1. The most intense vibrational transitions for each molecule are the torsions, with HOSH having a more intense transition of 72 km/mol compared to HSSH’s intensity of 14 km/mol. Furthermore, HOSH has a larger net dipole moment of 1.60 D compared to HSSH’s 1.15 D. While HOSH may be the more likely candidate of the two for possible astronomical observation via vibrational spectroscopy due to the notable difference in their intensities, both HSSH and HOSH have large enough net dipole moments to be detectable by rotational spectroscopy to discover the role these molecules may have as possible molecular sulfur sinks in the dense ISM.

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The challenging equilibrium structure of HSSH: Another success of the rotational spectroscopy / quantum chemistry synergism

Cited by 16 publications

References 75 publications

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Accuracy Meets Interpretability for Computational Spectroscopy by Means of Hybrid and Double-Hybrid Functionals

Spectral Signatures of Hydrogen Thioperoxide (HOSH) and Hydrogen Persulfide (HSSH): Possible Molecular Sulfur Sinks in the Dense ISM

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