Journal of Molecular Spectroscopy最新文献

{"title":"Theoretical study on the low-lying electronic states of SbF","authors":"Zhuozhao Li ,&nbsp;Linqiao Guo ,&nbsp;Lei Zhang ,&nbsp;Kai Wang ,&nbsp;Wenli Zou","doi":"10.1016/j.jms.2025.112011","DOIUrl":"10.1016/j.jms.2025.112011","url":null,"abstract":"<div><div>Multi-reference configuration interaction calculations are carried out to elucidate the distribution of low-lying valence and Rydberg states of antimony monofluoride (SbF) below 50000 cm⁻¹, where the effects of core–valence correlation and spin–orbit coupling have been employed. From the potential energy curves, the spectroscopic constants of seven (quasi-)bound <span><math><mi>Λ</mi></math></span>-S and fourteen (quasi-)bound <span><math><mi>Ω</mi></math></span> states have been derived, which agree well with the experimental values. Our results show that the second <span><math><mrow><msup><mrow></mrow><mrow><mn>3</mn></mrow></msup><mi>Π</mi></mrow></math></span> state involves the occupation on the Rydberg shell 6<span><math><mi>s</mi></math></span> of Sb, which settles the assignment of the so-called “<span><math><msub><mrow><mi>C</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span>” and “<span><math><mrow><msub><mrow><mi>C</mi></mrow><mrow><mn>3</mn></mrow></msub><mn>1</mn></mrow></math></span>” states in the ultraviolet spectra of SbF. With the help of the more accurate coupled cluster calculations, the dissociation energy (<span><math><msub><mrow><mi>D</mi></mrow><mrow><mi>e</mi></mrow></msub></math></span>) of SbF is determined to be 4.24 eV at the theoretical limit, being 0.2 eV smaller than the widely used empirical value in the literature.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"410 ","pages":"Article 112011"},"PeriodicalIF":1.4,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143830243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New spectroscopic fits and ab initio study of the O2(Σg−3)-SO2 (1A1) open-shell dimer","authors":"Wafaa M. Fawzy","doi":"10.1016/j.jms.2025.112010","DOIUrl":"10.1016/j.jms.2025.112010","url":null,"abstract":"&lt;div&gt;&lt;div&gt;We report the first accurate global fits for the rotation-spin-tunneling transitions in the microwave spectrum of the O&lt;sub&gt;2&lt;/sub&gt;(&lt;span&gt;&lt;math&gt;&lt;mmultiscripts&gt;&lt;msubsup&gt;&lt;mi&gt;Σ&lt;/mi&gt;&lt;mi&gt;g&lt;/mi&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;/msubsup&gt;&lt;mprescripts&gt;&lt;/mprescripts&gt;&lt;mspace&gt;&lt;/mspace&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/mmultiscripts&gt;&lt;/math&gt;&lt;/span&gt;)-SO&lt;sub&gt;2&lt;/sub&gt; (&lt;sup&gt;1&lt;/sup&gt;A&lt;sub&gt;1&lt;/sub&gt;) weakly bonded open-shell complex. In addition, we present a new ab initio investigation of the potential energy surface of O&lt;sub&gt;2&lt;/sub&gt;(&lt;span&gt;&lt;math&gt;&lt;mmultiscripts&gt;&lt;msubsup&gt;&lt;mi&gt;Σ&lt;/mi&gt;&lt;mi&gt;g&lt;/mi&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;/msubsup&gt;&lt;mprescripts&gt;&lt;/mprescripts&gt;&lt;mspace&gt;&lt;/mspace&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/mmultiscripts&gt;&lt;/math&gt;&lt;/span&gt;)-SO&lt;sub&gt;2&lt;/sub&gt;, using the UCCSD(T)/aug-cc-pV(n + d)Z level of theory where &lt;em&gt;n&lt;/em&gt; = 2 and 3. Analysis of the spectrum identified a-type and c-type transitions, frequencies of the a-type were not shifted while those of the c-type were shifted due to tunneling of the O&lt;sub&gt;2&lt;/sub&gt; and the SO&lt;sub&gt;2&lt;/sub&gt; moieties in the dimer. Only the A&lt;sub&gt;1&lt;/sub&gt; symmetric tunneling state was detected because the antisymmetric A&lt;sub&gt;2&lt;/sub&gt; state is not allowed by nuclear spin statistics in O&lt;sub&gt;2&lt;/sub&gt;-SO&lt;sub&gt;2&lt;/sub&gt;. Least squares fits with a standard deviation of 1 kHz were obtained using two computer codes incorporating semi-rigid rotor Hamiltonians that employ two different angular momenta coupling schemes. Results of the fits determined the effective tunneling frequency in the A&lt;sub&gt;1&lt;/sub&gt; symmetric state as &lt;span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;ν&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/msub&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt;= 2373.61134 &lt;span&gt;&lt;math&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;/math&gt;&lt;/span&gt;16 MHz, the electron spin coupling constant λ = 42,870.2186 &lt;span&gt;&lt;math&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;/math&gt;&lt;/span&gt;43 MHz, the rotational constants A = 7099.44 &lt;span&gt;&lt;math&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;/math&gt;&lt;/span&gt;33, B = 1528.886 &lt;span&gt;&lt;math&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;/math&gt;&lt;/span&gt;5, C = 1763.36 &lt;span&gt;&lt;math&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;/math&gt;&lt;/span&gt;6 MHz. The value of &lt;span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;ν&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/msub&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; equals the tunneling splitting (&lt;span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/msub&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt;) between the&lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mi&gt;A&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt; and &lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mi&gt;A&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt; symmetric tunneling states in the dimer, where the&lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mi&gt;A&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt; and &lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mi&gt;A&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt; levels are shifted in energy by &lt;span&gt;&lt;math&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;mfrac&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/mfrac&gt;&lt;msub&gt;&lt;mi&gt;ν&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/msub&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; and &lt;span&gt;&lt;math&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;mfrac&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/mfrac&gt;&lt;msub&gt;&lt;mi&gt;ν&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/msub&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt;, respectively. The ab initio study identified a global minimum energy structure of C&lt;sub&gt;1&lt;/sub&gt; symmetry and a metastable local minimum of C&lt;sub&gt;s&lt;/sub&gt; symmetry. We computed the optimized geometries of four equivalent configurations in the m","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"409 ","pages":"Article 112010"},"PeriodicalIF":1.4,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analysis of the rotational and hyperfine structure in the ‘red’ bands of ruthenium monoxide (RuO)","authors":"G.M. Chenard ,&nbsp;A.G. Adam ,&nbsp;D.W. Tokaryk ,&nbsp;C. Linton","doi":"10.1016/j.jms.2025.112007","DOIUrl":"10.1016/j.jms.2025.112007","url":null,"abstract":"<div><div>Laser Induced Fluorescence has been used to study the spectroscopy of Ruthenium Monoxide (RuO) in the UNB laser-ablation molecular-jet apparatus. High-resolution spectra of six bands from four previously obtained electronic transitions, [16.05]5 – X⁵Δ₄, [16.19]4 - X⁵Δ₄, [16.19]4 - X⁵Δ₃ and [15.07]3 - X⁵Δ₄ plus two previously unobserved transitions, [15.70]3 and [16.36]3 – X⁵Δ₄, were obtained at a resolution 20 times higher than previous experiments. This enabled rotational structure of six individual RuO isotopologues, ⁹⁶RuO, ⁹⁹RuO, ¹⁰⁰RuO, ¹⁰¹RuO, ¹⁰²RuO and ¹⁰⁴RuO to be well resolved and was used to examine detailed rotational and vibrational isotope effects. Hyperfine structure due to the nuclear spin <em>I</em> = 5/2 of ⁹⁹Ru and ¹⁰¹Ru has also been well resolved and was a valuable aid in establishing the electron configurations of the electronic states. The difference in the hyperfine structure in the [16.05]5 and [16.19]4 states supported their assignment as the Ω = 5 and 4 spin orbit components, ⁵Φ₅ and ⁵Φ₄, of a single Hund's case (a) electronic state.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"409 ","pages":"Article 112007"},"PeriodicalIF":1.4,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Two codes for calculation of the rotation-spin-tunneling energy levels in the microwave and the infrared spectra of O2 (Σg-3)-XY2 open-shell complexes","authors":"Wafaa M. Fawzy","doi":"10.1016/j.jms.2025.112008","DOIUrl":"10.1016/j.jms.2025.112008","url":null,"abstract":"<div><div>We developed new FORTRAN codes that employ two different Hamiltonians [Wafaa M. Fawzy, J. Mol. Spectrosc., 397, 111,822, 2023] for calculation of energy levels and relative intensities of rotational transitions in an asymmetric or a symmetric top weakly-bonded open-shell dimer. The type of complexes of interest consist of a polyatomic/diatomic closed-shell molecule and the O₂ diradical in its ground electronic state, where the monomers experience rotation-tunneling motion. The programs set up the Hamiltonian matrix considering pure rotation, quartic and sextic centrifugal distortion terms, electron-spin electron-spin coupling, R-dependence of electron-spin constants, electron-spin-rotation interaction, a symmetry treatment for rotation-tunneling of the monomers, and dependence of the rotational constants on the rotation-tunneling state. Numerical diagonalization of the total Hamiltonian matrix in the molecular basis set provides the eigenvalues and the eigenfunctions. The eigenfunctions are used to transform expectation values of the parity, five quantum numbers (&lt;P&gt;, &lt;K&gt;, &lt;N&gt;, &lt;P_s&gt;, &lt;Σ&gt;), and the electric dipole moment matrix elements from the Hamiltonian basis set to the eigenfunctions basis of the complex. Calculations showed that goodness of the quantum numbers depends on geometry and relative values of the electron–spin electron–spin coupling constants, the rotational parameters, the tunneling splitting. We used the Hellman–Feynman theory for calculation of derivatives of the eigenvalues with respect to molecular parameters, which significantly reduces the computer time for the non-linear least squares fits of transitions. The FORTRAN suites of computer programs were tested and validated by fitting the high resolution IR and MW spectra of the O₂–DF and the O₂-SO₂ dimers, respectively, with standard deviations within accuracy of the frequency measurement. However, the codes should be suitable for spectral analysis of any O₂ -XY₂ or O₂ -XY cluster, where XY₂ and XY represent a closed-shell non-linear triatomic molecule of C₂v symmetry (e.g. H₂O) and a diatomic entity (e.g. CO), respectively. The FORTRAN source programs, input and output files for spectral fits of the MW spectrum of O₂-SO₂ are discussed. In addition, zipped files of the suites of programs, the input and output files for fitting the MW spectrum of O₂-SO₂ and the IR spectrum of O₂ -DF, respectively, are provided as supplements that can be downloaded.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"409 ","pages":"Article 112008"},"PeriodicalIF":1.4,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oscillator strengths of the fundamental and overtone OH-stretching bands of tert-butyl hydroperoxide in gas phase","authors":"Casper Vindahl Jensen,&nbsp;Emil Vogt,&nbsp;Henrik G. Kjaergaard","doi":"10.1016/j.jms.2025.112009","DOIUrl":"10.1016/j.jms.2025.112009","url":null,"abstract":"<div><div>We have recorded gas-phase room-temperature absorption spectra of <em>t</em>-BuOOH in the OH-stretching regions, <span><math><mrow><mi>Δ</mi><msub><mrow><mi>v</mi></mrow><mrow><mi>O</mi><mi>H</mi></mrow></msub><mo>=</mo><mn>1</mn><mo>−</mo><mn>5</mn></mrow></math></span>, using a combination of Fourier transform infrared spectroscopy and cavity ring-down spectroscopy. The <em>t</em>-BuOOH samples are phase-extracted into dichloromethane, which can be accurately accounted for by spectral subtraction. We thereby obtain spectra of pure <em>t</em>-BuOOH and corresponding sample partial pressures allowing us to obtain absolute intensities of the OH-stretching bands in all regions. The subtraction of solvents and impurities provides accurate values for the band intensities and positions. A reduced dimensional local mode model is invoked to corroborate the experimentally determined band oscillator strengths and their assignments. The fundamental OH-stretching band oscillator strength is determined to be <span><math><mrow><mrow><mo>(</mo><mn>4</mn><mo>.</mo><mn>56</mn><mo>±</mo><mn>0</mn><mo>.</mo><mn>15</mn><mo>)</mo></mrow><mo>×</mo><mn>1</mn><msup><mrow><mn>0</mn></mrow><mrow><mo>−</mo><mn>6</mn></mrow></msup></mrow></math></span> about twice as large as the literature value. In the <span><math><mrow><mi>Δ</mi><msub><mrow><mi>v</mi></mrow><mrow><mi>O</mi><mi>H</mi></mrow></msub><mo>=</mo><mn>5</mn></mrow></math></span> region, the intensity is spread out efficiently by a Franck–Condon-like mechanism to combination features associated with the OH-stretch and the COOH-torsion.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"409 ","pages":"Article 112009"},"PeriodicalIF":1.4,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776793","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Empirical rovibrational energy levels for carbon disulfide","authors":"Tanvi Sattiraju,&nbsp;Jonathan Tennyson","doi":"10.1016/j.jms.2025.111998","DOIUrl":"10.1016/j.jms.2025.111998","url":null,"abstract":"<div><div>An analysis of the measured rovibrational transitions is carried out for the <span><math><msup><mrow></mrow><mrow><mn>12</mn></mrow></msup></math></span>C<span><math><msup><mrow></mrow><mrow><mn>32</mn></mrow></msup></math></span>S<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> isotopologue of carbon disulfide. Data from 21 sources is extracted and validated using a consistent set of standard linear molecule quantum numbers. A corrected list of 8714 CS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> transitions forms the input to a Measured Active Rotational–Vibrational Energy Levels (MARVEL) procedure, generating 4279 empirical rovibrational energy levels across 138 bands of <span><math><msup><mrow></mrow><mrow><mn>12</mn></mrow></msup></math></span>C<span><math><msup><mrow></mrow><mrow><mn>32</mn></mrow></msup></math></span>S<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>. Results are compared to the recent NASA Ames line list. While the agreement is generally good, issues are identified with the energy levels of some states, notably those with high values of the <span><math><msub><mrow><mi>v</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> bending quantum number.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"409 ","pages":"Article 111998"},"PeriodicalIF":1.4,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143529614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Direct potential fitting analysis for the A3Π1←X1Σ+ system of IBr","authors":"Tokio Yukiya,&nbsp;Shinji Kobayashi,&nbsp;Katsuki Nomura,&nbsp;Nobuo Nishimiya","doi":"10.1016/j.jms.2025.112006","DOIUrl":"10.1016/j.jms.2025.112006","url":null,"abstract":"<div><div>Doppler-limited vibrational absorption spectra of the <em>A</em> <span><math><mo>←</mo></math></span> <em>X</em> electronic transition of I<span><math><msup><mrow></mrow><mrow><mn>79</mn><mo>/</mo><mn>81</mn></mrow></msup></math></span>Br are measured in the 0.695 – <span><math><mrow><mn>0</mn><mo>.</mo><mn>735</mn><mspace></mspace><mi>μ</mi><mi>m</mi></mrow></math></span> and the 0.90 – <span><math><mrow><mn>0</mn><mo>.</mo><mn>94</mn><mspace></mspace><mi>μ</mi><mi>m</mi></mrow></math></span> region using a Ti:sapphire ring laser. The absorption lines belonging to <span><math><mrow><msup><mrow><mi>v</mi></mrow><mrow><mo>′</mo></mrow></msup><mo>←</mo><msup><mrow><mi>v</mi></mrow><mrow><mo>′</mo><mo>′</mo></mrow></msup><mo>=</mo><msup><mrow><mrow><mo>(</mo><mn>19</mn><mo>−</mo><mn>32</mn><mo>)</mo></mrow></mrow><mrow><mo>′</mo></mrow></msup></mrow></math></span> <span><math><mo>←</mo></math></span> (0,1)<span><math><msup><mrow></mrow><mrow><mo>′</mo><mo>′</mo></mrow></msup></math></span> and <span><math><msup><mrow><mrow><mo>(</mo><mn>2</mn><mo>,</mo><mn>3</mn><mo>,</mo><mn>4</mn><mo>)</mo></mrow></mrow><mrow><mo>′</mo></mrow></msup></math></span> <span><math><mo>←</mo></math></span> (6,7)<span><math><msup><mrow></mrow><mrow><mo>′</mo><mo>′</mo></mrow></msup></math></span> for I<span><math><msup><mrow></mrow><mrow><mn>79</mn><mo>/</mo><mn>81</mn></mrow></msup></math></span>Br are assigned, and the center position of the <span><math><mi>Q</mi></math></span> branch line belonging to over <span><math><msup><mrow><mi>v</mi></mrow><mrow><mo>′</mo></mrow></msup></math></span>=21, which is split into a doublet by the electric quadrupole coupling effect, was estimated. The potential models and function parameters for the <span><math><mrow><msup><mrow><mi>A</mi></mrow><mrow><mn>3</mn></mrow></msup><msub><mrow><mi>Π</mi></mrow><mrow><mn>1</mn></mrow></msub></mrow></math></span> and <span><math><mrow><msup><mrow><mi>X</mi></mrow><mrow><mn>1</mn></mrow></msup><msup><mrow><mi>Σ</mi></mrow><mrow><mo>+</mo></mrow></msup></mrow></math></span> states in I<span><math><msup><mrow></mrow><mrow><mn>79</mn><mo>/</mo><mn>81</mn></mrow></msup></math></span>Br were determined using direct potential fitting.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"409 ","pages":"Article 112006"},"PeriodicalIF":1.4,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143799037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rotational spectrum of trifluoroacetic acid: Extension of the measurements by chirped-pulse spectroscopy","authors":"Greta Naso ,&nbsp;Filippo Baroncelli ,&nbsp;Luca Evangelisti ,&nbsp;Assimo Maris ,&nbsp;Sonia Melandri","doi":"10.1016/j.jms.2025.111986","DOIUrl":"10.1016/j.jms.2025.111986","url":null,"abstract":"<div><div>The rotational spectrum of trifluoroacetic acid has been recorded at room temperature in the 18–26 GHz frequency range using a chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer. More than 180 new spectral lines have been identified and assigned to transitions within the vibrational ground state. A global fitting has been performed by incorporating spectroscopic data from previous studies, leading to the refinement of the molecular parameters. Two fitting models using Watson’s <span><math><mi>S</mi></math></span>-reduction and <span><math><mi>A</mi></math></span>-reduction are proposed, allowing the determination of <span><math><msub><mrow><mi>h</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> for the first model and <span><math><msub><mrow><mi>Φ</mi></mrow><mrow><mi>J</mi><mi>K</mi></mrow></msub></math></span>, <span><math><msub><mrow><mi>Φ</mi></mrow><mrow><mi>K</mi><mi>J</mi></mrow></msub></math></span>, and <span><math><msub><mrow><mi>ϕ</mi></mrow><mrow><mi>K</mi></mrow></msub></math></span> for the second one.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"408 ","pages":"Article 111986"},"PeriodicalIF":1.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143134418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rotational analyses of two transitions of WS near 13,100 cm−1, and further deperturbation analysis of the [15.30]1 – X 3Σ−0+ transition","authors":"Kristin N. Bales ,&nbsp;Dominik Kosican ,&nbsp;Jack C. Harms ,&nbsp;James J. O’Brien ,&nbsp;Leah C. O’Brien","doi":"10.1016/j.jms.2025.111999","DOIUrl":"10.1016/j.jms.2025.111999","url":null,"abstract":"<div><div>Two transitions of tungsten sulfide (WS) near 13,100 cm⁻¹, the (0,0) band of the [13.10]1 <strong>–</strong> <em>X</em> ³Σ⁻₀₊ transition and the (0,0) band of the [15.30]1 <strong>–</strong> <em>X</em> ³Σ⁻₁ transition, have been recorded at high resolution using intracavity laser absorption spectroscopy with a Fourier-transform spectrometer used for detection (ILS-FTS). The WS molecules were produced in the plasma discharge formed by applying 0.70–0.80 A of a discharge current from a pulsed DC plasma generator to a tungsten-lined copper hollow cathode. The reaction took place in the presence of Ar (∼70 %), H₂ (∼30 %), and CS₂ (∼0.1 %) gases at a total pressure of approximately 2 torr. Lines for all four abundant isotopologues of WS, ¹⁸²W³²S, ¹⁸³W³²S, ¹⁸⁴W³²S, and ¹⁸⁶W³²S, were measured and a rotational analysis was performed using PGOPHER. A constrained parameters approach was used to maintain expected mass relationships among isotopologues. This analysis increases the number of observed rotational levels from J ∼ 30 to J ∼ 100 for both excited states, allowing an increase in precision of spectroscopic constants. The new analysis of the [15.30]1 <strong>–</strong> <em>X</em> ³Σ⁻(1) transition enabled the reduced uncertainty in the previously determined value for the splitting of the 0+ and 1 Ω-components of the <em>X</em> ³Σ⁻ ground state. Also presented in this work is an expansion upon our earlier deperturbation analysis involving the [15.30]1 state to include the v′ = 2 vibrational level, which is perturbed by the v′ = 4 vibrational level of the [14.26]0⁺ state.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"408 ","pages":"Article 111999"},"PeriodicalIF":1.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143201823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Three-states model for calculating the X-X rovibrational transition intensities in hydroxyl radical (Erratum)","authors":"V.G. Ushakov,&nbsp;A.Yu. Ermilov,&nbsp;E.S. Medvedev","doi":"10.1016/j.jms.2025.111996","DOIUrl":"10.1016/j.jms.2025.111996","url":null,"abstract":"","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"408 ","pages":"Article 111996"},"PeriodicalIF":1.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}