The Potential Energy Coefficients for Internal Rotation in CH(2)DSH and CHD(2)SH

An internal axis method (IAM) has been used to determine the potential energy coefficients V(1), V(2), and V(3) to internal rotation in CH(2)DSH and CHD(2)SH. Two torsional differences for the gauche ground states and one torsional difference for the excited states were used to fix the V's. A fourth term, K(varsigma), 3(e(2))-2(o(2)), determines the torsional state assignment for this Q-branch series as o(2) to e(2) that was not known previously. For CH(2)DSH, the potential energy coefficients are V(1) = 4.54 cm(-1), V(2) = -9.36 cm(-1), V(3) = 440.50 cm(-1); for CHD(2)SH, V(1) = -4.12 cm(-1), V(2) = 8.23 cm(-1), V(3) = 439.65 cm(-1). Nonrigidity coefficients have also been determined for both the trans and gauche conformations of the ground state. Copyright 2001 Academic Press.     

Millimeter-Wave Spectra and Global Torsion-Rotation Analysis for the CH(3)OD Isotopomer of Methanol

New millimeter-wave and microwave measurements for CH(3)OD have been combined with previous literature data and with an extended body of Fourier transform far-infrared observations in a full global analysis of the first two torsional states (v(t) = 0 and 1) of the ground vibrational state. The fitted CH(3)OD data set contained 564 microwave and millimeter-wave lines and 4664 far-infrared lines, representing the most recent available information in the quantum number ranges J 相似文献   

The Far-Infrared Laser Magnetic Resonance Spectrum of CH2F

Far-infrared laser magnetic resonance (FIR-LMR) spectra due to the CH2F radical have been recorded on seven laser lines at wavelengths between 301 and 568 μm. Observed resonances were assigned to fine and hyperfine components of pure rotational transitions of CH2F in the ground vibrational state and the first excited state of the nu4 out-of-plane bending mode. All assigned transitions obey a-dipole selection rules. The data were combined with previously reported microwave results (Y. Endo, C. Yamada, S. Saito, and E. Hirota, J. Chem. Phys. 79, 1605 (1983)) and subjected to a least-squares fit to determine the parameters of the effective Hamiltonian describing the v4 = 0 and 1 vibrational levels of the CH2F radical. Copyright 1999 Academic Press.     

Description of the spectrum of the ethanol molecule with allowance for the mixing of its trans and gauche conformers

Based on symmetry methods, a rigorous model is, for the first time, obtained for describing the spectrum of the ethanol molecule CH₃CH₂OH in a given vibronic state with allowance for the mixing of its trans and gauche conformers due to the torsional motion of the hydroxyl group OH.     

Excited‐state hydrogen bonding dynamics of pyruvic acid and geminal‐diol, 2,2‐dihydroxypropanoic acid in aqueous solution: a DFT/TDDFT study

In this work, we present the optimized ground state geometrical structures, electronic excitation energies and corresponding oscillation strengths of the low‐lying electronically excited states for the isolated Tce‐CH3COCOOH and Tce‐CH3C(OH)2COOH as well as their corresponding hydrogen‐bonded dimers Tce‐CH3COCOOH‐H2O and Tce‐CH3C(OH)2COOH‐H2O through time‐dependent density functional theory method. It is found that the intermolecular hydrogen bonds C=O···H‐O are strengthened in the electronically excited states of the hydrogen‐bonded dimers Tce‐CH3COCOOH‐H2O and Tce‐CH3C(OH)2COOH‐H2O, in that the excitation energies of the related excited states for the hydrogen‐bonded dimers are decreased compared with those of the corresponding monomers. The calculated results are consistent with the rules that are first demonstrated by Zhao on the excited‐state hydrogen bonding dynamics. Copyright © 2012 John Wiley & Sons, Ltd.     

Internal Rotation of the Hydroxyl Group in Isopropanol and the Chirality of the Gauche Form: Fourier Transform Microwave Spectroscopy of (CH(3))(2)CHOD

The rotational spectrum of the deuterated isopropanol (CH(3))(2)CHOD has been observed by Fourier transform microwave spectroscopy and analyzed to yield tunneling splitting of 4431.4613 (17) MHz, between the antisymmetric and the symmetric gauche forms, which is much larger than the 2400 MHz estimated from the internal-rotation potential function reported in the literature. The potential function for the OH internal rotation has been examined in view of the discrepancy between the observed and estimated tunneling splitting, and it was accounted for by taking into account isotope effects on the potential constants. The deuterium quadrupole coupling effect has been included together with the Coriolis terms in the off-diagonal block of the Hamiltonian matrix for the gauche form. The deuterium quadrupole coupling constants obtained for the trans form were employed to calculate the components of the coupling constants as functions of the internal-rotation angle, and the components at around 120 degrees were compared with the values observed for the gauche form, thereby leading to unambiguous determination of the signs of the constants in the off-diagonal block; the signs are not obtainable from an ordinary analysis of the rotational spectra. The chirality of the gauche form was discussed by placing special emphasis on the effect of intermolecular interactions between two chiral molecules. Copyright 2001 Academic Press.     

Methyl barrier to internal rotation and evidence of torsion-torsion interaction in methyl thiolcyanoformate

The rotational spectrum of methyl thiolcyanoformate has been measured in the ground state and in four vibrationally excited states. The methyl group has the conformation syn with respect to the carbonyl group. The E component lines were assigned only in the ground state and the methyl group barrier to internal rotation has the value V₃ = 705 ± 20 cal/mole. The A species rotational transitions of the first excited state of the methyl and skeletal torsions do not follow a semirigid-rotor pattern probably because they strongly interact.     

Measurement and assignment of new FIR laser lines in12CH3OH and13CH3OH

We have found twelve new FIR laser lines in¹²CH₃OH and thirty three in¹³CH₃OH. Both molecules were pumped by a regular cw CO₂ laser. We have also assigned 20¹³CH₃OH laser lines to specific rotational energy levels in the excited C-O stretchhindered rotation combined states     

CH3与NO2的反应

用时间分辨傅立叶红外光谱法和量子化学计算，研究了CH3自由基与NO2的基元反应．由248 nm激光光解CH3Br或CH3I得到CH3自由基．首次观测到了振动激发的产物OH、HNO和CO2．另一产物NO也被证实．由此确定了反应通道CH3O+NO，CH2NO+OH 和HNO+H2CO．其中CH3O+NO是主要的反应通道．还用CCSD(T)/6-311++G(df,p)//MP2/6-311G(d,p)的方法对上述通道的机理在理论上做了研究．理论计算的结果与实验观察相符．     

Sub-Doppler Infrared Spectra of the OH-Stretch Fundamental of (13)C-Methanol

High-resolution infrared spectra of the (13)C-methanol OH stretching band, nu(1), were obtained by slit-jet absorption spectroscopy at a rotational temperature of 12-15 K. Twenty-eight subbands were assigned within the range of upper state quantum numbers, K' = 0 to 2 and J' = 0 to 10. The upper state energy levels are heavily perturbed; about half of the assigned subbands were found to be split by perturbations with matrix elements in the range 1-3 cm(-1). The doubled lines were deperturbed and together with the "unperturbed" lines were fitted to a global torsion-rotation Hamiltonian with root-mean-square deviation of 0.41 cm(-1) to yield a torsional barrier height of approximately 405 cm(-1) in the vibrationally excited state. Copyright 2000 Academic Press.     

Microwave spectra of dimethylsulfide-d6, (CD3)2S,ground and excited torsional states

The microwave spectra of the molecular isotope (CD₃)₂S in the ground state and the first and second excited states of methyl top torsion (internal rotation) and of CSC deformation as well as the ground-state spectra of the ¹³C and ³⁴S substituted forms have been measured. The rotational constants and centrifugal distortion and rotation-vibration interaction constants could be determined. The rotational lines in the excited torsional states (1₁, 1₂, 2₁, 2₂, 2₃) were found to be split into quartets due to the interaction between molecular rotation and methyl top internal rotation. The experimental multiplet splittings were fitted to those calculated from a rotation-internal rotation Hamiltonian in order to obtain values for the internal rotation barrier V₃ and the top-top interaction potential coefficients V₁₂ and V′₁₂. V₁₂ was too highly correlated with V₃ for a separate determination. The values following from the least-squares adjustment are discussed.     

Stark spectroscopy of 13CD3OH with the HCN laser

The laser Stark spectrum of ¹³CD₃OH has been studied using the 311 μm line of the HCN laser. An extensive series of absorption lines has been observed and assigned to the J = 3 to 11 members of the K = 2 ← 3E₁, Q-branch transition in the v_t = 1 excited torsional state. Zero-field frequencies for all the assigned transitions are given with improved accuracy over those calculated from available molecular constants. For the Q-branch series, the branch origin and the series expansion coefficients are also presented.     

Global fit of rotational transitions of methyl formate (HCOOCH3) in the ground and first excited torsional states

The microwave spectrum of methyl formate (HCOOCH₃) has been observed in the frequency range from 7 to 200 GHz. New 348 lines were assigned to E-species in the first excited torsional state. By combining these lines with previously reported data, a global analysis of A- and E-species lines of the ground and first excited torsional states were carried out on the basis of the internal axis method. A total of 3862 transitions were fitted to a Hamiltonian model involving 69 molecular parameters to a weighted unitless standard deviation of 1.96.     

甲烷-空气预混火焰中OH∗,CH∗发光的定量测量及模拟

基于燃烧化学自发光的诊断技术对发动机诊断、监控有重要意义.针对碳氢燃料燃烧中OH*,CH*激发态物质的生成机理,及其与释热率、当量比的关系进行了实验与模拟探究.首先,利用提出的辐射标定手段对当量比0.7~1.33范围内甲烷-空气预混火焰进行了化学发光量化测量,通过波长分辨的光学收集系统,同时获得各发光组分的浓度,具有很强的便利性.然后采用一维燃烧反应模拟,对与实验工况相同条件下的发光辐射进行定量计算,并对比了释热分布与激发态物质（OH*,CH*,C₂*,CO₂*）的相互关系,计算结果表明,在甲烷-空气层流火焰中,OH*,CH*最合适标识释热率,C₂*次之,CO₂*与释热率分布几乎无相关性.通过实验与计算的对比结果,分析了现有OH*,CH*的各反应通道和常数的准确度,并评估了两自发光组分的主要生成反应路径.      

AC等离子体辅助CH4低温氧化的分子激发作用

本文采用实验测量和数值模拟结合的方法,对AC放电下He/CH4/O2混合气中激发态对甲烷裂解和低温氧化的动力学贡献进行研究。基于HP-Mech,增加反应物的放电机理以及激发态参与的化学反应及其驰豫反应,建立CH4低温氧化机理。采用化学反应动力学求解器CHEMKIN中的两段式Plasma-PSR模型模拟放电过程及化学反应过程。该动力学模型能较好地预测反应物的消耗和主要产物的生成,反应路径分析表明激发态物质CH4(v),O2(v),O2(a^1△g)等通过链式反应CH4(v)+OH→CH3+H2O,O2(v)+H→OH+O,O2(a^1△g)+H→OH+O促进活性自由基和产物的生成。     

(NH_2CH_2COOH)_2CdCl_2晶体的拉曼光谱的研究

（ＮＨ２ＣＨ２ＣＯＯＨ）２ＣｄＣｌ２晶体的拉曼光谱的研究刘建军吴粤郑吉民扈士芬蓝国祥（南开大学天津３０００７１）ＲａｍａｎＳｐｅｃｔｒａｏｆ（ＮＨ２ＣＨ２ＣＯＯＨ）２ＣｄＣｌ２ＣｒｙｓｔａｌｓＬｉｕＪｉａｎｊｕｎ，ＷｕＹｕｅ，ＺｈｅｎｇＪｉｍｉｎ，Ｈ...     

532 nm激光作用下CH3I分子的多光子电离

利用飞行时间质谱仪在超声射流冷却条件下探讨了532 nm激光作用下CH3I分子的多光子电离(MPI)解离过程和机制,得到了分子的飞行时间质谱,质谱中包含较强的I 、CH3 离子信号和较弱的CH3I 、CHn (n≤2)、C 、H 离子信号.不同激光能量下的质谱信号在排布上相似,但在强度上有差别.在532 nm激光作用下CH3I分子的多光子电离包括两个过程:一是CH3I分子由双光子激发到A带解离,生成I原子和CH3基团,然后再吸收光子实现中性碎片电离;另一通道是CH3I分子由三光子共振激发到里德堡C态,处于激发态的母体分子继续吸收两个光子电离形成母体离子,碎片离子可由母体离子解离形成.     

The rotational spectrum of methoxyethyne: Centrifugal distortion and internal rotation analysis

In the rotational spectrum of methoxyethyne 173 new transitions (J ≤ 30) have been measured between 150 and 240 GHz. In the centimeter range 25 new transitions (J ≤ 11) of the first excited torsional state have also been assigned. An overall fit of the measurements using a structure relaxation model has allowed us to accurately determine the internal rotation parameters. For the A substate effective rotational parameters are given which allow the calculation of transition frequencies of possible astrophysical interest.     

Microwave spectrum of dimethylallene excited states and strong Coriolis coupling

The rotational spectra of six excited vibrational states of dimethylallene were measured and assigned to the corresponding vibrational levels, and for three more excited state spectra at least the rotational constants could be determined. Between the two lowest excited levels of symmetry species b₂ and b₁ of group C_2v a strong a-type Coriolis coupling was found to exist. The evaluation of the resulting perturbation by a diagonalization of the energy matrix yielded ζ^(a) = 0.36 and a precise value for the vibrational energy difference 48.761 GHz (1.6 cm^?1). The state b₂ is believed to be the first excited torsional substate (01, 10)₁ of methyl internal rotation, and the rotational transitions of this state as well as those of the strongly coupled state b₁ presented very irregular multiplet splittings. On the other hand, the splittings of the next-higher excited state of species a₂ which could be identified as the partner torsional substate (01, 10)₂, followed the regular pattern, yielding an internal rotation barrier V₃ (2079 cal/mole) not unlike that derived earlier from ground state splittings.     

发射光谱法研究甲基环己烷燃烧时激发态自由基时间历程

采用三组单色仪探测系统,测量了甲基环己烷在高温反射激波作用下瞬态燃烧反应过程中三种激发态自由基OH*,CH*和C*₂的特征光辐射,得到了激发态自由基时间历程和光辐射相对强度随温度的变化规律。反射激波温度1 200～1 700 K,激波压力1.5 atm,甲基环己烷摩尔分数0.1%,当量比1.0。在点火燃烧初始阶段三种自由基几乎同时产生,自由基持续时间随着温度的升高而变短。相同温度下CH*和OH*自由基持续时间大于C*₂自由基,在1 400 K以下C*₂自由基发光消失。OH*和CH*自由基发光强度在T<1 400 K时对温度变化不敏感,而在T>1 400 K时CH*自由基峰值随温度快速增长,C*₂和OH*峰值随温度增大比较平缓。将实验结果和化学反应机理模拟结果进行了对比,实验获得的OH*自由基时间历程在低温时和机理预测结果吻合较好,但在高温时有一定差异。CH*自由基时间历程在高温与机理结果吻合较好,在低温时机理预测结果CH*自由基持续时间要长于实验结果。实验测得的结果为含激发态物种化学反应动力学机理的验证和优化提供了依据。