Journal of Molecular Spectroscopy最新文献

英文中文

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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

Theoretical studies at the M06-2X/aug-cc-pVDZ level combined with experimental spectroscopy, were employed to investigate the intermolecular interactions between bromopentafluorobenzene (C₆F₅Br) and triethylenediamine (DABCO). The C₆F₅Br 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.

采用M06-2X/ augg -cc- pvdz水平的理论研究结合实验光谱研究了溴五氟苯（C6F5Br）与三乙二胺（DABCO）的分子间相互作用。同时具有σ空穴和π空穴的C6F5Br分子作为电子受体，与DABCO的氮原子形成分子间相互作用。计算结果和分析显示，形成了两种不同的二聚体和四种三聚体，通过σ-空穴⋯n卤素键和/或π-空穴⋯n键稳定，相互作用能范围为−5.50至−18.50 kcal/mol，表明形成了中等强度的非共价键。能量分解分析（EDA）量化了驱动力，结果表明静电相互作用占总吸引力的34 - 49%，而色散力和轨道项分别占27 - 58%和8 - 25%。分子原子量子理论（QTAIM）和非共价相互作用（NCI）分析证实了这些相互作用的存在和性质。实验红外和拉曼光谱测量提供了关键的验证。观察到的位移证实了分子复合物的形成。这些实验位移与计算得到的配合物光谱一致。这项工作为研究相互竞争的σ-空穴和π-空穴相互作用提供了基本的见解，并将为相关超分子体系的合理设计提供有价值的框架。

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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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

High-resolution rovibrational spectroscopy of the ν₁ (10⁰0 ← 00⁰0) band of ¹⁴N¹⁵N¹⁶O 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, J-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-J 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.

利用量子级联激光空腔衰荡光谱仪（QCL-CRDS）在7.8 μm中红外波段对14N15N16O的ν1（1000←0000）波段进行了高分辨率的旋转振动光谱分析。给出了32个跃迁的第一个实验空气和自展宽系数，显示出明显的旋转依赖性。通过有效的碰撞参数，包括碰撞截面、碰撞直径和碰撞松弛时间，进一步研究了碰撞动力学。对二元碰撞微扰现象进行系统的j依赖分析有助于阐明外来分子和自相互作用机制。测量了32次跃迁的线强度。值得注意的是，5条高j r支系（R70、R71、R72、R78、R79）首次被测得，并显示出系统的旋转依赖性。对于这些跃迁，推导了爱因斯坦A系数、振子强度和跃迁偶极矩，并评估了描述旋转振动相互作用的赫尔曼-沃利斯系数。总之，这些量化参数加深了我们对这种线性非中心对称分子的旋转振动相互作用机制的理解。计算了该振动带对应的光谱常数，如带中心、旋转常数和离心畸变常数。这些详细的分子参数量化和光谱研究对一氧化二氮的同位素研究具有重要意义，对大气和天体物理研究具有重要意义。

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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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

Microwave spectra of jet-cooled bromoacetic acid (CH₂BrCOOH) and chloroacetic acid (CH₂ClCOOH) 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 in the plane. 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 ⁷⁹Br and ⁸¹Br 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 same 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.

得到了喷冷溴乙酸（CH2BrCOOH）和氯乙酸（CH2ClCOOH）的微波光谱。对于溴乙酸，观察到的光谱明确地归属于C-Br键几乎垂直于其他重原子所定义的平面的构象。这与先前在室温下观察到的构象不同，其中发现C-Br键在平面内。MP2和DFT计算预测了四种稳定的构象，观测到的构象与计算能量最低的构象相对应。确定了79Br和81Br核四极耦合张量的对角线和非对角线元素，并与计算结果相吻合。有趣的是，之前对氯乙酸的室温研究也揭示了C-Cl键在平面内的构象（即类似于对溴乙酸的室温研究）。因此，为了观察在室温和喷气冷却条件下观察到的构象之间是否存在相同的差异，我们还对喷气冷却氯乙酸的光谱进行了检查。在这种情况下，在射流中观察到的构象与之前在室温下报道的相同（平面内C-Cl键）。然而，所得到的光谱常数比以前确定的和在这里报告的要精确一些。由于超音速膨胀中的冷却作用，本研究中观察到的物质可能是两种酸的最低能量形式。与先前对氟，氯和溴乙酸的研究比较，突出了这些系统的复杂构象景观。

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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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Journal of Molecular Spectroscopy

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

Saurabh Mishra

Non-covalent interactions such as hydrogen bonding and π–π stacking are central to molecular architecture. This study investigates the indole dimer near the band origin at 35238 cm⁻¹ using IR-UV double resonance spectroscopy and DFT calculations. The IDIR spectrum shows a red-shifted NH stretch at 3420 cm⁻¹, indicative of hydrogen bonding. Computational analyses with B97D and B3LYP-D3 functionals favor N–H‧‧‧π bonded structures. Among these, we assign a tilted geometry featuring N–H‧‧‧π interaction as the most consistent with experimental observations. The broad spectral profile also suggests the coexistence of multiple low-energy isomers.

非共价相互作用，如氢键和π -π堆叠是分子结构的核心。本研究利用IR-UV双共振光谱和DFT计算研究了35238 cm−1波段附近的吲哚二聚体。红外光谱显示在3420 cm−1处有一个红移的NH拉伸，表明存在氢键。用B97D和B3LYP-D3进行计算分析，有利于N-H···π键结构。其中，我们认为具有N-H··π相互作用的倾斜几何形状与实验观测最一致。广谱图也表明存在多种低能异构体。

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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

Line intensities of the

14 N 2

16 O

molecule are calculated using the DVR3D nuclear-motion program suite. Recently, we (Mizus et al., JQSRT, 344, 109463 (2025)) presented a potential energy surface (PES) fitted to empirical energy levels with an accuracy close to 0.002

{cm}^{- 1}

and very accurate dipole moment surfaces (DMS) calculated ab initio 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 (

v_{1} v_{2} ℓ v_{3}

) equals (5000), (4200), (3200) and (0112), whose intensities have been measured with sub-percent accuracy.

用DVR3D核运动软件计算了14N2 16O分子的谱线强度。最近，我们（Mizus et al.， JQSRT, 344, 109463(2025)）提出了一个与经验能级拟合的势能面（PES），精度接近0.002 cm−1，以及使用MRCI（多参考配置相互作用）理论从头开始计算的非常精确的偶极矩面（DMS）。然而，这些精确的PES和DMS并没有产生均匀准确的计算线强度：一些过渡强度与测量值有数量级的差异。在这里，我们分析了这些不准确计算线强度的原因，并开发了一个光谱模型，该模型给出了一贯准确的强度预测。这一改进是基于PES精度的相对较小的改进，通过将计算中使用的内部坐标从Jacobi改为Radau来强调这一需要。特别是，新模型预测的线强度与实验精度接近，这些振动带，即（v1v2, v3）等于（5000），（4200），（3200）和（0112），其强度测量精度低于百分之一。

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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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

Pure rotational transitions of three isomers of the cyanovinoxy radical were observed by Fourier-transform microwave spectroscopy. Fine and hyperfine components observed in the spectra were fully analyzed to determine their precise molecular constants. Cyano-substitution effect on the electronic structure of the vinoxy radical is discussed based on the experimentally determined molecular constants.

用傅里叶变换微波光谱法观察了三种氰氧基异构体的纯旋转跃迁。对光谱中观察到的精细和超精细组分进行了充分的分析，确定了它们的精确分子常数。根据实验测定的分子常数，讨论了氰基取代对乙烯基电子结构的影响。

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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

The (0,0) and (0,1) bands of the A1 – X0⁺ and B1 – X0⁺ transitions of tungsten monoxide (WO) have been recorded in high resolution using intracavity laser absorption spectroscopy techniques (ILS and ILS-FTS). Lines for all four abundant isotopologues, ¹⁸²WO, ¹⁸³WO, ¹⁸⁴WO, and ¹⁸⁶WO, are observed and have been rotationally analyzed and fit using a constrained-variables approach in PGOPHER. While these transitions have been previously described in the literature, this new analysis incorporates all four isotopologues and presents evidence for an avoided crossing interaction between the v = 0 vibrational levels of the A1 and B1 states. New values for spectroscopic constants that incorporate the perturbation interactions are presented and compared to literature results.

利用腔内激光吸收光谱技术（ILS和ILS- fts）高分辨率地记录了一氧化钨（WO） A1 - X0+和B1 - X0+跃迁的（0,0）和（0,1）波段。我们观察了182WO、183WO、184WO和186WO这四种丰富同位素的谱线，并利用PGOPHER中的约束变量方法进行了旋转分析和拟合。虽然这些转变已经在以前的文献中描述过，但这项新的分析包含了所有四种同位素，并提供了A1和B1态的v = 0振动水平之间避免交叉相互作用的证据。提出了包含摄动相互作用的光谱常数的新值，并与文献结果进行了比较。

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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

The impact of alkali metal ions (Li⁺, Na⁺, and K⁺) on the structure and vibrations in metal ion-diglycine complexes with up to two water molecules (M⁺GlyGly-nH₂O) is examined using cryogenic infrared action spectroscopy, conformer-specific IR-IR spectroscopy, H₂O/D₂O isotopic substitution experiments, and scaled, harmonic DFT calculations. While the main conformer is identical for all metal ions for the bare complex (M⁺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⁺ than for the K⁺ ion. The number of solvent molecules needed to change the initial peptide conformation differs between the metal ions and is smaller for Li⁺ 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.

碱金属离子（Li+， Na+和K+）对金属离子-二甘氨酸配合物（M+GlyGly-nH2O）的结构和振动的影响通过低温红外作用光谱，构象特异性IR-IR光谱，H2O/D2O同位素取代实验和缩放谐波DFT计算进行了研究。虽然裸配合物（M+GlyGly）中所有金属离子的主构象是相同的，但在加水时观察到的构象取决于金属离子的性质，并且溶剂化对Li+的影响明显大于K+离子。改变初始肽构象所需的溶剂分子数在金属离子之间是不同的，Li+比较大的金属离子要少。对连续加水后的光谱进行比较，揭示了溶剂化如何影响这些簇中金属离子的电场强度。在所有情况下，水分子的加入降低了金属离子与肽之间相互作用的强度，因此，降低了肽中诱导的电场强度。

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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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

This study presents an experimental determination of spectroscopic parameters for the less-abundant isotopologues ⁴²CaF and ⁴⁴CaF, alongside ⁴⁰CaF, by high resolution laser-induced fluorescence spectroscopy in a skimmed free jet expansion. We recorded spectra near the natural linewidth limit and derived spectroscopic constants for both

X^{2} Σ^{+}

and

A^{2} Π

states, including the fine and ¹⁹F magnetic hyperfine parameters. We also estimated the r(⁴⁴Ca/⁴⁰Ca) isotope amount ratio, demonstrating the potential use of optical spectroscopy for isotope analysis.

本文提出了用高分辨率激光诱导荧光光谱法测定低丰度同位素物42CaF和44CaF以及40CaF的光谱参数的实验方法。我们记录了接近自然线宽极限的光谱，并推导了X2Σ+和A2Π状态的光谱常数，包括精细和19F磁超精细参数。我们还估计了r（44Ca/40Ca）同位素量比，证明了光学光谱在同位素分析中的潜在应用。

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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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

Λ

-S and fourteen (quasi-)bound

Ω

states have been derived, which agree well with the experimental values. Our results show that the second

^{3} Π

state involves the occupation on the Rydberg shell 6

s

of Sb, which settles the assignment of the so-called “

C_{2}

” and “

C_{3} 1

” states in the ultraviolet spectra of SbF. With the help of the more accurate coupled cluster calculations, the dissociation energy (

D_{e}

) 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.

利用核价相关和自旋轨道耦合效应，对50000 cm−1以下单氟化锑（SbF）的低洼价态和Rydberg态的分布进行了多参考组态相互作用计算。由势能曲线推导出7个（准）束缚态Λ-S和14个（准）束缚态Ω的光谱常数，与实验值吻合较好。我们的结果表明，第二个3Π态涉及Sb的Rydberg壳层6s的占据，它解决了SbF紫外光谱中所谓的“C2”和“C31”态的分配。借助更精确的耦合簇计算，确定SbF的解离能（De）在理论极限为4.24 eV，比文献中广泛使用的经验值小0.2 eV。

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引用次数: 0

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