Journal of Molecular Spectroscopy最新文献_第3页

Theoretical and experimental verifications of intermolecular σ-hole⋯n and π-hole⋯n interactions between bromopentafluorobenzene and triethylenediamine 溴五氟苯与三乙二胺分子间σ-空穴⋯n和π-空穴⋯n相互作用的理论和实验验证

IF 1.3 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-12-01 Epub Date: 2025-10-04 DOI: 10.1016/j.jms.2025.112053

Dong Xie , Jing-Jing You , Xin-Ting He , Hao Qiu , Zhe-Rui Zhang , Ge Gao , Weichun Ye , Bing Han , Pan-Pan Zhou , Zhaoyong Yang

{"title":"Theoretical and experimental verifications of intermolecular σ-hole⋯n and π-hole⋯n interactions between bromopentafluorobenzene and triethylenediamine","authors":"Dong Xie , Jing-Jing You , Xin-Ting He , Hao Qiu , Zhe-Rui Zhang , Ge Gao , Weichun Ye , Bing Han , Pan-Pan Zhou , Zhaoyong Yang","doi":"10.1016/j.jms.2025.112053","DOIUrl":"10.1016/j.jms.2025.112053","url":null,"abstract":"<div><div>Theoretical studies at the M06-2X/aug-cc-pVDZ level combined with experimental spectroscopy, were employed to investigate the intermolecular interactions between bromopentafluorobenzene (C<sub>6</sub>F<sub>5</sub>Br) and triethylenediamine (DABCO). The C<sub>6</sub>F<sub>5</sub>Br molecule possessing both σ-hole and π-hole regions acts as an electron acceptor and forms intermolecular interactions with the nitrogen atoms of DABCO. Computational results and analyses revealed the formation of two distinct dimers and four trimers stabilized via σ-hole⋯n halogen bonds and/or π-hole⋯n bonds with interaction energies ranging from −5.50 to −18.50 kcal/mol, indicating the formation of moderately strong non-covalent bonds. Energy decomposition analysis (EDA) quantified the driving forces, showing that electrostatic interactions contribute to 34–49 % the total attraction, while dispersion forces and orbital terms account for 27–58 % and 8–25 %, respectively. The existence and nature of these interactions were confirmed by Quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) analyses. Experimental IR and Raman spectroscopy measurements provided crucial validation. The formation of molecular complexes was confirmed by observed shifts. These experimental shifts are in agreement with the calculated spectra of the complexes. This work provides fundamental insights into competing σ-hole and π-hole interactions and would offer a valuable framework for the rational design of related supramolecular systems.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"413 ","pages":"Article 112053"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145266659","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}

引用次数: 0

High-resolution cavity ring-down spectroscopic investigation of the fundamental symmetric stretch (ν1) band of 14N15N16O isotopologue in the 7.8 μm mid-IR region 7.8 μm中红外区14N15N16O同位素体基本对称伸展（ν1）带的高分辨率空腔衰荡光谱研究

IF 1.3 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-12-01 Epub Date: 2025-11-08 DOI: 10.1016/j.jms.2025.112056

Soumyadipta Chakraborty, Indrayani Patra, Arup Biswas, Manik Pradhan

{"title":"High-resolution cavity ring-down spectroscopic investigation of the fundamental symmetric stretch (ν1) band of 14N15N16O isotopologue in the 7.8 μm mid-IR region","authors":"Soumyadipta Chakraborty, Indrayani Patra, Arup Biswas, Manik Pradhan","doi":"10.1016/j.jms.2025.112056","DOIUrl":"10.1016/j.jms.2025.112056","url":null,"abstract":"<div><div>High-resolution rovibrational spectroscopy of the ν<sub>1</sub> (10<sup>0</sup>0 ← 00<sup>0</sup>0) band of <sup>14</sup>N<sup>15</sup>N<sup>16</sup>O has been performed using a quantum cascade laser–based cavity ring-down spectrometer (QCL-CRDS) operating in the 7.8 μm mid-infrared region. The first experimental air- and self-broadening coefficients for 32 transitions are presented, showing a distinct rotational dependence. Collisional dynamics were further examined through effective collision parameters, including collision cross sections, collision diameters, and collision relaxation times for the probed transitions. A systematic, <em>J</em>-dependent analysis on the binary collisional perturbation phenomena facilitated elucidation of the foreign molecular and self-interaction mechanisms. Line intensities were measured for 32 transitions. Notably, five high-<em>J</em> R-branch lines (R70, R71, R72, R78, R79) were measured for the first time, and a systematic rotational dependence was demonstrated. For these transitions, Einstein A coefficients, oscillator strengths, and transition dipole moments were derived, and Herman–Wallis coefficients describing rovibrational interaction were evaluated. Together, these quantified parameters deepen our comprehension of the rovibrational interaction mechanisms in this linear non-centrosymmetric molecule. The spectroscopic constants, such as band center, rotational constant, and centrifugal distortion constant corresponding to this vibrational band, were also calculated. These detailed molecular parameter quantifications and spectroscopic investigations are significant for isotopic studies of nitrous oxide and have important implications for atmospheric and astrophysical research.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"413 ","pages":"Article 112056"},"PeriodicalIF":1.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145525400","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}

引用次数: 0

Microwave spectra of jet-cooled bromo- and chloroacetic acids 喷射冷却溴乙酸和氯乙酸的微波光谱

IF 1.4 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-08-01 Epub Date: 2025-07-11 DOI: 10.1016/j.jms.2025.112033

Kenneth J. Koziol, Aaron J. Reynolds, Victor Drewanz, Luis R. Padilla Jr., Kenneth R. Leopold

{"title":"Microwave spectra of jet-cooled bromo- and chloroacetic acids","authors":"Kenneth J. Koziol, Aaron J. Reynolds, Victor Drewanz, Luis R. Padilla Jr., Kenneth R. Leopold","doi":"10.1016/j.jms.2025.112033","DOIUrl":"10.1016/j.jms.2025.112033","url":null,"abstract":"<div><div>Microwave spectra of jet-cooled bromoacetic acid (CH<sub>2</sub>BrCOOH) and chloroacetic acid (CH<sub>2</sub>ClCOOH) have been obtained. For bromoacetic acid, the observed spectra are definitively assigned to a conformer in which the C–Br bond is nearly perpendicular to the plane defined by the other heavy atoms. This differs from the conformer previously observed at room temperature in which the C–Br bond was found to be <em>in the plane</em>. MP2 and DFT calculations predict four stable conformations, and the observed form corresponds to that with the lowest calculated energy. Diagonal and off-diagonal elements of the <sup>79</sup>Br and <sup>81</sup>Br nuclear quadrupole coupling tensors have been determined and are in good agreement with the calculations. Interestingly, previous room temperature work on chloroacetic acid also revealed the conformation in which the C–Cl bond is in-plane (i.e., analogous to the room temperature work on bromoacetic acid). Thus, to see if the same disparity exists between the conformers observed under room temperature and jet-cooled conditions, the spectrum of jet-cooled chloroacetic was also examined. In this case, the conformer observed in the jet was the <em>same</em> as that previously reported at room temperature (in-plane C–Cl bond). The spectroscopic constants obtained, however, are somewhat more accurate than those previously determined and are reported here. Due to the cooling in the supersonic expansion, the species observed in this work are likely the lowest-energy forms for both acids. Comparison with prior studies on fluoro-, chloro-, and bromoacetic acids highlights a complex conformational landscape for these systems.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"411 ","pages":"Article 112033"},"PeriodicalIF":1.4,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144653280","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}

引用次数: 0

Exploring indole dimer structures at the band origin: A spectroscopic gas phase IR analysis 在带源处探索吲哚二聚体结构：光谱气相红外分析

IF 1.4 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-08-01 Epub Date: 2025-07-09 DOI: 10.1016/j.jms.2025.112031

Saurabh Mishra

引用次数: 0

Calculated 14N2 16O line intensities using Radau coordinates and an accurate potential energy surface 利用Radau坐标和精确势能面计算14N2 - 16O线强度

IF 1.3 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-08-01 Epub Date: 2025-07-26 DOI: 10.1016/j.jms.2025.112034

Irina I. Mizus , Mikhail A. Rogov , Nikolai F. Zobov , Roman I. Ovsyannikov , Evgenii I. Lebedev , Jonathan Tennyson , Oleg L. Polyansky

{"title":"Calculated 14N2 16O line intensities using Radau coordinates and an accurate potential energy surface","authors":"Irina I. Mizus , Mikhail A. Rogov , Nikolai F. Zobov , Roman I. Ovsyannikov , Evgenii I. Lebedev , Jonathan Tennyson , Oleg L. Polyansky","doi":"10.1016/j.jms.2025.112034","DOIUrl":"10.1016/j.jms.2025.112034","url":null,"abstract":"<div><div>Line intensities of the <span><math><mrow><mn>14</mn><mtext>N</mtext><mn>2</mn></mrow></math></span> <span><math><mrow><mn>16</mn><mtext>O</mtext></mrow></math></span> molecule are calculated using the DVR3D nuclear-motion program suite. Recently, we (Mizus <em>et al.</em>, JQSRT, <strong>344</strong>, 109463 (2025)) presented a potential energy surface (PES) fitted to empirical energy levels with an accuracy close to 0.002 <span><math><msup><mrow><mtext>cm</mtext></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span> and very accurate dipole moment surfaces (DMS) calculated <em>ab initio</em> using a MRCI (multi-reference configuration interactions) level of theory. However, these accurate PES and DMS did not yield uniformly accurate calculated line intensities: some transition intensities disagreed with the measured ones by orders of magnitude. Here we analyze the reasons for these inaccurately calculated line intensities and develop a spectroscopic model which gives consistently accurate intensity predictions. This improvement is based on a relative minor improvement in the accuracy of the PES, the need for which was highlighted by changing the internal coordinates used in the calculation from Jacobi to Radau. In particular, the new model predicts line intensities with close to experimental accuracy for those vibrational bands, namely (<span><math><mrow><msub><mrow><mi>v</mi></mrow><mrow><mn>1</mn></mrow></msub><msub><mrow><mi>v</mi></mrow><mrow><mn>2</mn></mrow></msub><mi>ℓ</mi><msub><mrow><mi>v</mi></mrow><mrow><mn>3</mn></mrow></msub></mrow></math></span>) equals (5000), (4200), (3200) and (0112), whose intensities have been measured with sub-percent accuracy.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"411 ","pages":"Article 112034"},"PeriodicalIF":1.3,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144809614","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}

引用次数: 0

Fourier-transform microwave spectroscopy of cyano-substituted vinoxy radicals 氰基取代的乙烯基自由基的傅里叶变换微波光谱

IF 1.3 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-08-01 Epub Date: 2025-08-07 DOI: 10.1016/j.jms.2025.112035

Masakazu Nakajima , Yasuki Endo

引用次数: 0

Deperturbation analysis of an avoided crossing in the A1 v = 0 and B1 v = 0 states of WO WO在A1 v = 0和B1 v = 0状态下避免交叉的解扰分析

IF 1.4 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-06-01 Epub Date: 2025-05-28 DOI: 10.1016/j.jms.2025.112022

Kristin N. Bales , Akhila Swarna , James J. O'Brien , Leah C. O'Brien

引用次数: 0

Impact of the metal ion and microsolvation on the structure and vibrations in a small model peptide 金属离子和微溶剂化对小模型肽结构和振动的影响

IF 1.4 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-06-01 Epub Date: 2025-05-16 DOI: 10.1016/j.jms.2025.112021

K.A.E. Meyer, E. Garand

{"title":"Impact of the metal ion and microsolvation on the structure and vibrations in a small model peptide","authors":"K.A.E. Meyer, E. Garand","doi":"10.1016/j.jms.2025.112021","DOIUrl":"10.1016/j.jms.2025.112021","url":null,"abstract":"<div><div>The impact of alkali metal ions (Li<sup>+</sup>, Na<sup>+</sup>, and K<sup>+</sup>) on the structure and vibrations in metal ion-diglycine complexes with up to two water molecules (M<sup>+</sup>GlyGly-<em>n</em>H<sub>2</sub>O) is examined using cryogenic infrared action spectroscopy, conformer-specific IR-IR spectroscopy, H<sub>2</sub>O/D<sub>2</sub>O isotopic substitution experiments, and scaled, harmonic DFT calculations. While the main conformer is identical for all metal ions for the bare complex (M<sup>+</sup>GlyGly), the conformers observed upon the addition of water are dependent on the nature of the metal ion and the impact of solvation is distinctly larger for the Li<sup>+</sup> than for the K<sup>+</sup> ion. The number of solvent molecules needed to change the initial peptide conformation differs between the metal ions and is smaller for Li<sup>+</sup> than for the larger metal ions. The comparison of the spectra upon the sequential addition of water reveals how solvation impacts the electric field strength of the metal ions in these clusters. In all cases, the addition of water molecules reduces the strength of the interaction between the metal ion and the peptide and consequently, reduces the strength of the electric field induced in the peptide.</div></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"410 ","pages":"Article 112021"},"PeriodicalIF":1.4,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144168695","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}

引用次数: 0

A molecular beam study of the (0,0)A2Π←X2Σ+ band of CaF isotopologues CaF同位素物（0,0）A2Π←X2Σ+带的分子束研究

IF 1.4 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-06-01 Epub Date: 2025-06-16 DOI: 10.1016/j.jms.2025.112023

Termeh Bashiri , Phelan Yu , Nicholas R. Hutzler , Timothy C. Steimle , Carlos Abad , Mitchio Okumura

引用次数: 0

Theoretical study on the low-lying electronic states of SbF 关于 SbF 低洼电子态的理论研究

IF 1.4 4区物理与天体物理

Journal of Molecular Spectroscopy Pub Date : 2025-06-01 Epub Date: 2025-04-11 DOI: 10.1016/j.jms.2025.112011

Zhuozhao Li , Linqiao Guo , Lei Zhang , Kai Wang , Wenli Zou

{"title":"Theoretical study on the low-lying electronic states of SbF","authors":"Zhuozhao Li , Linqiao Guo , Lei Zhang , Kai Wang , 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<sup>−1</sup>, 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":"2025-06-01","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}

引用次数: 0