Journal of Molecular Spectroscopy最新文献_第2页

First high-resolution study of vanadium deuteride (VD): The C′5Δ–X5Δ (0,0) and (1,0) bands 氘化钒（VD）的首次高分辨率研究：C ' 5Δ-X5Δ（0,0）和（1,0）波段

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

Journal of Molecular Spectroscopy

Pub Date : 2025-11-29 DOI: 10.1016/j.jms.2025.112058

Nathan T. Brandes, Nicholas J. Ihrke, Thomas D. Varberg

The first electronic spectrum of gas-phase vanadium monodeuteride (VD) has been recorded and analyzed, extending recent work on vanadium hydride (VH). Two vibrational bands of a parallel transition were observed and assigned as the C′⁵Δ–X⁵Δ (0,0) and (1,0) bands, with origins at 13,030 and 13,907 cm⁻¹. High-resolution laser excitation spectra, supported by dispersed fluorescence measurements, permitted determination of rotational, spin–orbit, spin–rotation, and Λ-doubling constants for the X⁵Δ (v = 0–2) and C′⁵Δ (v = 0–1) states. The dispersed fluorescence spectra revealed the first two excited vibrational levels of the ground state, giving ωₑ = 1179.86(57) cm⁻¹ and ωₑxₑ = 12.47(21) cm⁻¹. Multiple local perturbations were identified in both upper-state vibrational levels and interpreted in terms of nearby Σ and orbitally degenerate states. Comparison with corresponding VH data confirmed isotopic scaling relations for rotational and fine-structure parameters, validating the assignments and effective-Hamiltonian analysis. These measurements complete the first systematic spectroscopic coverage of the 3d transition-metal hydrides, enabling direct isotopic comparisons across the series. They also provide new benchmark data for testing ab initio models and guiding future astronomical searches for VH and VD in cool stellar and substellar atmospheres.

对气相一氘化钒（VD）的第一电子谱进行了记录和分析，扩展了最近对氢化钒（VH）的研究。观测到两个平行跃迁的振动带，并将其命名为C ' 5Δ-X5Δ（0,0）和（1,0）带，其起源分别为13,030和13,907 cm−1。在分散荧光测量的支持下，高分辨率激光激发光谱允许确定X5Δ （v = 0-2）和C ' 5Δ （v = 0-1）态的旋转、自旋轨道、自旋旋转和Λ-doubling常数。分散荧光光谱显示了基态的前两个激发振动能级，ωₑ= 1179.86(57)cm−1和ωₑxₑ= 12.47(21)cm−1。在两个高状态振动水平上确定了多个局部扰动，并根据附近的Σ和轨道简并态进行了解释。与相应的VH数据比较，确定了旋转和精细结构参数的同位素标度关系，验证了分配和有效哈密顿分析。这些测量完成了第一个三维过渡金属氢化物的系统光谱覆盖，使整个系列的同位素直接比较成为可能。它们还为从头算模型的测试提供了新的基准数据，并指导未来在冷恒星和亚恒星大气中对VH和VD的天文搜索。

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引用次数: 0

Study on two-stage concentration detection algorithm based on UV-DOAS: For mixed gas of NO and SO2 基于UV-DOAS的NO和SO2混合气体两级浓度检测算法研究

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

Journal of Molecular Spectroscopy

Pub Date : 2025-11-10 DOI: 10.1016/j.jms.2025.112057

Bo Peng , Haiwang Liu , Anran Zhang , Lei Zheng , Qi Deng , Mi Zhu , Ningsheng Liao , Zhen Tang , Ye Tao

Nitric oxide (NO) and sulfur dioxide (SO₂) are common atmospheric pollutants. Monitoring these gases from fixed-source emissions is crucial for environmental assessments and air quality control. To address spectral overlap issues in the ultraviolet differential absorption spectra of NO and SO₂ mixed gas, this study proposes a two-stage deep learning algorithm based on bidirectional long short-term memory network (Bi-LSTM) combined with attention mechanism. First, frequency domain filtering is applied to the differential optical density (DOD) signal of the mixed gas (200–230 nm wavelength range) to remove high-frequency noise. Then, the spectral separation model decomposes the filtered signal into single-component DOD for NO and SO₂. Finally, a dedicated single-component concentration detection model is used to detect the concentration from its respective DOD. The results demonstrate that the proposed two-stage algorithm resolves mutual interference between SO₂ and NO and effectively separated the DOD of two single-component gases. It achieves superior concentration detection precision compared to traditional segmented method and one-stage detection methods. For the concentration detection of mixed gas, the detection limits for SO₂ and NO are 0.06 ppm and 0.16 ppm, respectively, with corresponding uncertainties of 0.31 % and 0.78 %. This study is expected to be widely applied in the field of multi-component gas detection, contributing to public health and environmental protection.

一氧化氮（NO）和二氧化硫（so2）是常见的大气污染物。监测固定源排放的这些气体对于环境评估和空气质量控制至关重要。针对NO和SO₂混合气体紫外差异吸收光谱中的光谱重叠问题，本研究提出了一种基于双向长短期记忆网络（Bi-LSTM）结合注意机制的两阶段深度学习算法。首先，对混合气体（200 ~ 230 nm波长范围）的差分光密度（DOD）信号进行频域滤波，去除高频噪声；然后，光谱分离模型将滤波后的信号分解为NO和so2的单分量DOD。最后，使用专用的单组分浓度检测模型从其各自的DOD检测浓度。结果表明，该两阶段算法解决了so2和NO之间的相互干扰，有效地分离了两种单组分气体的DOD。与传统的分段法和一级检测方法相比，具有更高的浓度检测精度。混合气体的浓度检测，SO2和NO的检出限分别为0.06 ppm和0.16 ppm，不确定度分别为0.31%和0.78%。该研究有望在多组分气体检测领域得到广泛应用，为公众健康和环境保护做出贡献。

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引用次数: 0

Fourier transform microwave spectrum of the CO-propylene oxide complex co -环氧丙烷配合物的傅里叶变换微波谱

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

Journal of Molecular Spectroscopy

Pub Date : 2025-11-09 DOI: 10.1016/j.jms.2025.112054

Yoshiyuki Kawashima , Eizi Hirota

The rotational spectrum of the carbon monoxide-propylene oxide (CO-PO) complex was measured in the frequency region from 5 up to 24 GHz by Fourier transform microwave spectroscopy. For the normal species 55 a-type and 19 c-type transitions were observed, while b-type transition was not observed. Enriched ¹³CO and C¹⁸O samples were employed to record a-type and c-type transitions for the complexes with the respective isotopologues CO bound to PO. All the observed transition frequencies were analyzed for the normal species using a CH₃ group internal rotation and overall rotation Hamiltonian. The potential barrier height V₃ to internal rotation of the CH₃ group was determined to be 855.07 (81) cm⁻¹. The rotational constants derived for CO-PO complex led to the structure in which the CO moiety was located in one side of the PO ether plane opposite to that of the CH₃ group, namely an anti-conformer. The intermolecular bonding of CO-PO was found to be stronger to that of Ar-PO and weaker than that of CO₂-PO; by assuming a Lennard-Jones-type potential, the force constant of the van der Waals stretching mode and the dissociation energy were estimated to be 2.7 Nm⁻¹ and 3.4 kJmol⁻¹, respectively.

用傅里叶变换微波光谱法测定了一氧化碳-环氧丙烷（CO-PO）配合物在5 ~ 24 GHz频率范围内的旋转光谱。正常种a型转变55株，c型转变19株，b型转变未发生。富集的13CO和C18O样品分别记录了CO与PO结合的配合物的a型和c型转变。用CH3基团内旋和全旋哈密顿量分析了正常种的所有跃迁频率。测定CH3基团的内旋势垒高度V3为855.07 (81)cm−1。CO-PO配合物的旋转常数导致CO部分位于与CH3基团相反的PO醚面一侧的结构，即反构象。CO-PO的分子间键比Ar-PO强，比CO2-PO弱；假设为lennard - jones型势，计算得到van der Waals拉伸模式的力常数为2.7 Nm−1，解离能为3.4 kJmol−1。

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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 : 2025-11-08 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

Study on the spectral characteristics for singlet states transitions of MgO MgO单线态跃迁的光谱特性研究

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

Journal of Molecular Spectroscopy

Pub Date : 2025-11-04 DOI: 10.1016/j.jms.2025.112055

Junxia Cheng , Bo Tian , Zixin Zhang , Tian Bai , Jia Wang , Shenjiang Wu

The spectral radiation characteristics of metal oxides of diatomic molecules are particularly important for celestial detection, target identification and tracking, combustion control and diagnosis, thermal design of protective systems, etc. Ultraviolet spectrum is a way of energy transfer, and it is also a way of signal transmission, which is very important in many fields of basic research. This paper mainly studies the transition spectra of optical material MgO under ultraviolet transitions. Potential energy curves and transition dipole moments were investigated, which was combined to obtain spectral parameters such as transition probability, energy level lifetime, wavelength and intensity of transition systems. The high temperature spectral were provided and compared of different transition. These studies provide more theoretical basis and experimental reference for the study of UV transition spectral characteristics of metal molecules.

双原子分子金属氧化物的光谱辐射特性对天体探测、目标识别与跟踪、燃烧控制与诊断、防护系统热设计等具有重要意义。紫外光谱是能量传递的一种方式，也是信号传输的一种方式，在许多基础研究领域中占有重要地位。本文主要研究了光学材料MgO在紫外跃迁下的跃迁光谱。通过对势能曲线和跃迁偶极矩的研究，得到了跃迁系统的跃迁概率、能级寿命、波长和强度等光谱参数。给出了不同转变的高温光谱，并对其进行了比较。这些研究为金属分子紫外跃迁光谱特性的研究提供了更多的理论依据和实验参考。

引用次数: 0

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