Journal of Molecular Spectroscopy最新文献_第2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 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Journal of Molecular Spectroscopy

Pub 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

A new electronic transition of vanadium hydride: The C′5Δ–X5Δ (1,0) band 氢化钒的一个新的电子跃迁：C ' 5Δ-X5Δ（1,0）带

IF 1.3 4区物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Journal of Molecular Spectroscopy

Pub Date : 2025-09-10 DOI: 10.1016/j.jms.2025.112051

Kevin A. Tovar , Thomas D. Varberg

We report the observation and analysis of a new electronic transition in gas-phase vanadium hydride (VH), identified as the C′⁵Δ–X⁵Δ (1,0) band with an origin at 14,015 cm⁻¹ (714 nm). The spectrum was recorded by laser excitation spectroscopy, with laser-induced fluorescence detected to the X⁵Δ (v = 1) level. Dispersed fluorescence measurements enabled a detailed characterization of the vibrationally excited ground state, yielding a vibrational interval of ΔG_1/2 = 1606.6(2) cm⁻¹. Despite the presence of significant local perturbations—particularly in the Ω = 0 and 1 spin components of the C′⁵Δ state—a full rotational analysis of the spectrum using a Hund's case (a) Hamiltonian was achieved. Spectroscopic constants including rotational, spin–orbit, spin–rotation, and Λ-doubling parameters are reported for both the new C′⁵Δ state and the X⁵Δ (v = 1) level. Additionally, we observed a small local perturbation in the X⁵Δ₁ (v = 1) level near J = 9, attributed to homogeneous spin–orbit and heterogeneous L-uncoupling interactions with the previously analyzed A⁵Π (v = 0) state. An X⁵Δ ∼ A⁵Π coupled Hamiltonian was used to model this perturbation and yielded interaction parameters roughly consistent with semi-empirical estimates. This work represents only the second analyzed spectroscopic transition of gas-phase VH.

我们报道了对气相氢化钒（VH）中一个新的电子跃迁的观察和分析，该跃迁被确定为C ' 5Δ-X5Δ（1,0）带，其起源为14,015 cm−1 （714 nm）。用激光激发光谱法记录光谱，激光诱导荧光检测到X5Δ （v = 1）级。分散荧光测量使振动激发基态的详细表征，产生的振动间隔ΔG1/2 = 1606.6(2) cm−1。尽管存在显著的局部扰动，特别是在C ' 5Δ态的Ω = 0和1自旋分量中，使用洪德情况(a)哈密顿量对光谱进行了全面的旋转分析。本文报道了新的C ' 5Δ态和X5Δ （v = 1）能级的光谱常数，包括旋转、自旋轨道、自旋旋转和Λ-doubling参数。此外，我们在J = 9附近的X5Δ 1 （v = 1）能级观察到一个小的局部扰动，这归因于与先前分析的A5Π （v = 0）态的均匀自旋轨道和非均匀l -解耦相互作用。使用X5Δ ~ A5Π耦合哈密顿量来模拟这种扰动，并得到与半经验估计大致一致的相互作用参数。这项工作只代表了第二次分析气相VH的光谱转变。

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引用次数: 0

Measurements of the microwave spectrum and calculations of the molecular structure for η4-butadiene osmium tricarbonyl 四丁二烯锇三羰基的微波光谱测量及分子结构计算

IF 1.3 4区物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Journal of Molecular Spectroscopy

Pub Date : 2025-09-09 DOI: 10.1016/j.jms.2025.112050

Adam M. Daly , Stephen G. Kukolich

The microwave spectrum of η⁴-butadiene osmium tricarbonyl was measured in the 6–12 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the ¹⁹²Os isotopologues were determined to have the following values: A = 939.4(2), B = 849.08(1) and C = 816.71(1) MHz. The centrifugal distortion constant is D_J = 0.60(7) kHz. 16 a-dipole transitions were measured and included in the fit. Extensive high-level G16 calculations were made using DFT methods with various basis sets, including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). The best calculated values are in very good agreement with the experimental values.

利用flygere - balle型脉冲束傅立叶变换微波（FTMW）光谱仪，在6-12 GHz频率范围内测量了η - 4-丁二烯锇三羰基的微波光谱。测定了192o同位素物的旋转常数：A = 939.4(2), B = 849.08(1), C = 816.71(1) MHz。离心畸变常数DJ = 0.60(7) kHz。测量了16个偶极子跃迁，并将其纳入拟合。广泛的高水平G16计算使用DFT方法与各种基集，包括核心电位（ECP）。采用B3LYP/def2-QZVPP，采用Gaussian 16计算最佳结构，其中包含一个核心电位（ECP）。最佳计算值与实验值符合得很好。

引用次数: 0

Off-axis integrated cavity output spectroscopic study of 31112–01101 band of CO2 in 1.57 μm spectral region CO2在1.57 μm光谱区31112-01101波段的离轴集成腔输出光谱研究

IF 1.3 4区物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Journal of Molecular Spectroscopy

Pub Date : 2025-09-04 DOI: 10.1016/j.jms.2025.112049

Ayan Kumar Pal , Naveen Kumar

The near-infrared experimental investigation of greenhouse gases and their spectroscopic parameters finds a wide range of applications in the field of atmospheric science, astrophysics, and climate change research. Carbon dioxide (CO₂), an important greenhouse gas, has been the subject of various spectroscopic studies due to its pivotal role in climate change, as well as in the atmospheric and astrophysical sciences. In this study, we present the spectroscopic investigation of ro-vibrational lines of P- and R-branches of the weak 31112–01101 band (f-symmetry) of CO₂ lying in 1.57 μm spectral region. The study was carried out by high-sensitive off-axis integrated cavity output spectroscopy (OA-ICOS) coupled with a continuous wave-external cavity diode laser (CW-ECDL) source. The study focuses on the experimental measurement of vital spectroscopic parameters, such as air-broadening coefficients (γ_air), line intensities and self-broadening coefficients (γ_self) of various interference free lines (8 ≤ J ≤ 28) in the P- and R-branches of the hot band. The OA-ICOS absorption lines were modeled using the Voigt profile function to retrieve the parameters, which accurately reproduced the line shapes within the spectral noise level. The obtained γ_air were compared with empirical values present in HITRAN2020 and theoretical values in CDSD, showing mean discrepancies of about 3.20% and 1.25%, respectively. The retrieved line intensities and γ_self were also compared with previously reported values, revealing mean discrepancies of about 1.99% and 1.34%, respectively. Additionally, rotational dependency, the Einstein-A₂₁ coefficient, effective collision diameter and cross-sections for CO₂-CO₂ and CO₂-air binary systems have also been explored and presented. The molecular spectroscopic parameters retrieved in this study will find various applications in the field of atmospheric science, astrophysical science, and climate change research.

温室气体及其光谱参数的近红外实验研究在大气科学、天体物理学和气候变化研究领域有着广泛的应用。二氧化碳（CO2）是一种重要的温室气体，由于其在气候变化以及大气和天体物理科学中的关键作用，一直是各种光谱研究的主题。本文研究了CO2在1.57 μm光谱区31112-01101弱波段（f对称）的P支和r支的反振动谱线。研究采用高灵敏度离轴集成腔输出光谱（OA-ICOS）与连续波外腔二极管激光器（CW-ECDL）光源耦合进行。重点研究了热带P和r分支中各种无干扰谱线（8≤J≤28）的空气展宽系数（γair）、谱线强度和自展宽系数（γself）等重要光谱参数的实验测量。利用Voigt剖面函数对OA-ICOS吸收谱线进行建模，提取参数，准确再现了光谱噪声水平内的吸收谱线形状。将所得的γ - air与HITRAN2020中的经验值和CDSD中的理论值进行比较，平均差异分别约为3.20%和1.25%。将检索到的线强度和γself与先前报道的值进行比较，发现平均差异分别约为1.99%和1.34%。此外，还探讨了CO2-CO2和co2 -空气二元系统的旋转依赖性、Einstein-A21系数、有效碰撞直径和横截面。本研究获取的分子光谱参数将在大气科学、天体物理科学、气候变化研究等领域得到广泛应用。

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引用次数: 0

Rotational spectroscopy, quadrupole coupling and unusual quartic centrifugal distortion constants of 1,1-dichloro-1-silacyclopent-2-ene 1,1-二氯-1-硅环戊烯的旋转光谱、四极耦合和异常的四次离心畸变常数

IF 1.3 4区物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Journal of Molecular Spectroscopy

Pub Date : 2025-08-25 DOI: 10.1016/j.jms.2025.112038

Alexander R. Davies , Nicole T. Moon , Amanda J. Duerden , Thomas M.C. McFadden , Gamil A. Guirgis , G.S. Grubbs II

The ground state rotational spectrum of 1,1-dichloro-1-silacyclopent-2-ene has been recorded using chirped-pulse Fourier transform microwave spectroscopy. A planar ring-structure in the ground vibrational state is supported by the rotational spectrum, but particularly by the analysis of the sometimes-complicated hyperfine splitting and isotopic substitution. Furthermore, fitting the rotational spectrum to a Watson S-reduced Hamiltonian in the I^r representation yields a negative value of D_J, which is in agreement with quantum chemical calculation. In addition, the quadrupole coupling is considered and some structural information is presented — both compare well to expectations from other related systems and quantum chemical calculation.

用啁啾脉冲傅立叶变换微波光谱法记录了1,1-二氯-1-硅环-2-烯的基态旋转光谱。旋转谱支持了在地面振动状态下的平面环结构，特别是对有时复杂的超精细分裂和同位素取代的分析。此外，将旋转谱拟合到Ir表示中的沃森s -约简哈密顿量会产生负的DJ值，这与量子化学计算一致。此外，还考虑了四极耦合，并给出了一些结构信息，两者都与其他相关系统和量子化学计算的期望相比较。

引用次数: 0

Updated line list for the principal isotopologue of carbon monoxide 更新了一氧化碳主要同位素物的清单

IF 1.3 4区物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Journal of Molecular Spectroscopy

Pub Date : 2025-08-22 DOI: 10.1016/j.jms.2025.112037

Vladimir G. Ushakov, Emile S. Medvedev

The line list for the principal isotopologue of CO calculated earlier by the present authors (Medvedev, 2022), (Ushakov, 2022) with the irregular dipole-moment function (DMF) is updated with use of the recent high-precision measurements in the 3-0 (Bielska et al., 2022, Hodges et al., 2025) and 7-0 (Balashov et al., 2023) bands. The new data came in contradiction with the experimental data on the 1-0 band (Zou and Varanasi, 2002, Devi et al., 2018). Therefore, we performed fitting several model DMFs to the modified original data set of Meshkov et al. (2022) by including the new above-referenced data and by excluding the data for the 1-0 band. The updated line list is calculated with the irregular DMF. In particular, excellent agreement with recent high-level ab initio calculations on the 3-0 band (Bielska et al., 2022) is emphasized and predictions for the 1-0 and 8-0 bands are outlined. In the new update of the HITRAN database (Gordon et al., 2025) new high-precision measurements in the cold and hot fundamental bands are announced. When these data are published, they will be compared with the predictions of our new line list.

本文作者（Medvedev, 2022）、（Ushakov, 2022）利用不规则偶极矩函数（DMF）计算出的CO主同位素谱线列表，使用最近在3-0波段（Bielska等人，2022年，Hodges等人，2025年）和7-0波段（Balashov等人，2023年）进行的高精度测量进行了更新。新数据与1-0波段的实验数据相矛盾（Zou和Varanasi， 2002, Devi et al., 2018）。因此，我们对Meshkov et al.（2022）修改后的原始数据集进行了几个模型dmf的拟合，包括新的上述参考数据，并排除了1-0波段的数据。用不规则DMF计算更新后的行表。特别强调了与最近在3-0波段的高级从头计算（Bielska et al., 2022）的良好一致性，并概述了1-0和8-0波段的预测。在最新更新的HITRAN数据库（Gordon et al., 2025）中，宣布了在冷和热基本波段进行的新的高精度测量。当这些数据公布后，它们将与我们的新产品线列表的预测进行比较。

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引用次数: 0

Investigating the temperature dependence of photoelectron spectra in KArn clusters: Insights into stable structures and spectroscopic properties 研究KArn簇中光电子能谱的温度依赖性：对稳定结构和光谱性质的见解

IF 1.3 4区物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Journal of Molecular Spectroscopy

Pub Date : 2025-08-07 DOI: 10.1016/j.jms.2025.112032

Slim Awali , Salem Naili , Jamila Dhiflaoui , Hamid Berriche , Abdelaziz Bouazizi

In this article, we investigate the temperature dependence of the photoelectron spectrum of a potassium atom adsorbed on argon clusters

{Ar}_{n}

(n

= 1 - 10

). We employ a combined Monte Carlo (MC) method with basin-hopping global optimization to simulate the geometries of the argon clusters in the excited 4p state at temperature

T

. Our ab initio model utilizes appropriate pseudopotentials to replace the core electrons of

K^{+}

and all electrons of the argon atoms, along with core polarization potentials. Electronic energies and transition dipole moments are calculated for each selected geometry, enabling us to simulate the photoelectron spectrum. Our results highlight the significant impact of temperature on the spectral characteristics of photoelectrons emitted from the

K Ar

system. At a temperature of 5 K, we observe that the stable structures better reproduce the experimental photoelectron spectra. As the temperature increases, we observe broadening and shifting of the spectral peaks, suggesting the successive evaporation of argon atoms. Additionally, the influence of spin–orbit coupling is examined, which may also affect the spectral features and the dynamics following excitation.

在本文中，我们研究了吸附在氩簇Arn （n =1−10）上的钾原子的光电子能谱的温度依赖性。我们采用蒙特卡罗（MC）方法和跳槽全局优化来模拟温度t下4p激发态氩簇的几何形状。我们的从头算模型利用适当的伪势来取代K+的核心电子和氩原子的所有电子，以及核心极化势。电子能量和跃迁偶极矩为每个选择的几何计算，使我们能够模拟光电子能谱。我们的结果强调了温度对KAr系统发射的光电子光谱特性的显著影响。在5 K的温度下，我们观察到稳定的结构能更好地再现实验光电子能谱。随着温度的升高，我们观察到光谱峰的展宽和移动，表明氩原子的连续蒸发。此外，研究了自旋-轨道耦合的影响，它也可能影响谱特征和激发后的动力学。

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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 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 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

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 : 2025-07-11 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