1,2,4-三唑-3-羧酸溶液的拉曼光谱研究（英文）

本文实验测量了1,2,4-三唑-3-羧酸根(TC~-阴离子)及其环去质子化衍生物(dp-TC~2-二价阴离子)在水溶液中的拉曼光谱,并采用MN15泛函和PCM溶剂模型计算了其几何结构、振动频率和拉曼强度.基于计算光谱和氘化位移的测量,对dp-TC~(2-)的拉曼光谱做了清楚的光谱标识.本文还系统研究了TC~-阴离子的各种质子互变异构体,发现2H互变异构体比其他互变异构体更稳定,并且TC~-溶液的实验拉曼光谱与单体2H互变异构体的计算光谱也基本一致.与计算光谱相比,实验观测到的谱带分裂可能来自于TC~-的氢键结合二聚体的影响.     

ZrO-双原子阴离子的光电子成像谱

利用激光溅射制备了ZrO^-双原子阴离子,测量了其光电子成像谱．实验观测到的光电子能谱可以在光学光谱和高精度从头计算的基础上得到很好的归属．ZrO^-的基态确定为²△态,其自旋-轨道分裂能为578±12 cm^-1,ZrO的电子亲和能测定为1.249±0.005 eV．第一次在实验上观测到ZrO的c³∑^-激发态,其相对于X¹∑⁺基态的能量为13316±24 cm^-1,同时还对ZrO与其等电子体NbN的电子结构进行了比较．     

飞秒时间分辨拉曼光谱用于研究β-胡萝卜素单重激发态内转换和振动弛豫过程

搭建了飞秒时间分辨受激拉曼光谱(FSRS)装置，并用于研究全反式β-胡萝卜素单重电子激发态超快内转换和振动弛豫过程.基于三脉冲“抽运-探测”方案搭建的时间分辨受激拉曼光谱装置同时实现了150fs的时间分辨率和23.7cm^-1的光谱分辨率，光谱检测范围为300—4000cm^-1.对全反式β-胡萝卜素电子激发态的飞秒时间分辨拉曼光谱研究表明，β-胡萝卜素被激发到S₂态后，经由寿命约为0.3ps的中间态S_X态实     

AgO分子C2∏-X2∏(0,0)带高分辨光谱再研究

本文利用激光诱导荧光技术对AgO分子C²∏-X²∏(0,0)带光谱在∽0.02 cm^-1分辨率水平开展了高分辨研究. 在超声射流条件下利用银针电极对O₂/Ar混合气高压放电制备AgO分子，利用自行研制的窄线宽单纵模光参量振荡器作为可调谐激光光源，实验记录了同位素分辨的¹⁰⁷Ag¹⁶O和¹⁰⁹Ag¹⁶O分子C²∏-X²∏(0,0)带的高分辨光谱. 通过对实验光谱的转动分析获得了两个同位素分子的精确光谱常数，其中¹⁰⁷Ag¹⁶O分子C²∏态常数为首次实验测定. 结合文献和理论计算，实验观测的C²∏态自旋-轨道耦合效应很可能来自于与四重解离态⁴Σ^-或⁴∏的态混合.     

钒氧卟啉正负离子的结构畸变与电子-振动耦合的DFT研究

用PBE1PBE方法研究了钒氧卟啉一价阴离子([VOP]^-)、一价阳离子([VOP]⁺)的单态和三重态结构. 结果表明[VOP]^-和[VOP]⁺的最稳定电子态均为三重态,其未配对电子一个占据钒的d_xy轨道,另一个占据卟啉环的π轨道,因此两者均为π-自由基. 中性分子(VOP)的双重态最稳定,其未配对电子占据钒的d_xy轨道. 双重态VOP具有较高的C_4v对称性,而三重态[VOP]^- 离子由于发生姜-泰勒效应对称性降低为C_2v. 计算了[VOP]^-姜-泰勒活性振动模式的电子-振动耦合常数,并用前线KS轨道的节面分布解释了姜-泰勒畸变沿特定简正模式发生的原因. 三重态[VOP]⁺ 阳离子的卟啉环发生键长交替变化,构型畸变起源于电子态近简并引起的赝姜-泰勒效应,导致其对称性从C_4v降低为C₄,其结构变化可以用重组的前线KS轨道的节面分布解释.     

普适的基于能量的分块方法计算甲烷水合物簇的精确结合能和拉曼光谱

甲烷水合物在化学、能源和环境科学等领域中都具有重要作用. 本文采用普适的基于能量的分块(GEBF)方法计算了多种甲烷水合簇的结合能和拉曼光谱. 首先使用这些甲烷水合簇的在显相关耦合簇[CCSD(T)(F12^*)]水平下得到的GEBF结合能,评估了一系列密度泛函计算的结果. 计算结果表明B3PW91-D3和B97D泛函表现最佳,与GEBF-CCSD(T)(F12^*)基准相比的平均绝对误差分别仅为0.27和0.47 kcal/mol. 然后用GEBF-B3PW91-D3方法计算得到了单、双笼甲烷水合簇的结构和拉曼光谱,得到的甲烷C-H键伸缩拉曼振动峰与实验值的偏差小于3 cm^-1,说明B3PW91-D3泛函可以很好地重现实验结果. 随着水笼尺寸的增加. 甲烷C-H键伸缩拉曼峰发生红移,该现象与实验中提出的“松笼-紧笼”模型吻合. 此外,甲烷分子邻近环境(水笼)的改变对拉曼光谱的影响很小,环境从单笼变为双笼导致C-H键伸缩拉曼振动峰的蓝移不超过3 cm^-1. 甲烷水合簇的理论拉曼光谱与实验拉曼光谱结合可以用来研究海底或星际冰体内部的甲烷水合物的结构. 结合B3PW91-D3或B97D泛函和机器学习模型,可以进一步应用分子动力学模拟研究甲烷水合物的成核/生长机制和相变过程.     

3-二甲氨基-2-甲基丙烯醛S2激发态结构动力学 (cited: 3)

采用共振拉曼光谱和完全活性自洽场理论计算研究了3-二甲氨基-2-甲基丙烯醛(DMAMP)光激发到S₂(ππ^*)态后的光物理性能．在B3LYP/6-311++G(d,p)水平计算确定了DMAMP与其三种异构体之间的基态异构化能垒,指认了振动光谱．采用涵盖紫外强吸收带的激光波长,获得了DMAMP在环己烷、乙腈和甲醇溶剂中的A-带共振拉曼光谱,含时密度泛函方法计算确定了该光谱中基频的相对强度,发现振动-电子耦合发生在S₂(ππ^*)态的Franck-Condon区域．CASSCF计算方法确定低单重和三重激发态、势能面锥形交叉点和系间窜跃点的激发能．共振拉曼光谱强度模式分析和CASSCF计算获得了DMAMP的A-带短时结构动力学和其后的衰变动力学表明,C1=O6和C2=C3之间的瞬时去共轭效应发生在S₂(ππ^*)态的Franck-Condon区域,激发态电荷重分布机制表明,C3和二甲氨基之间以及C1和C2之间的共轭增强效应发生在波包离开Franck-Condon区域后．C1=O6和C2=C3之间的去共轭效应使得-C3=N(CH₃)₂沿着C2-C3键旋转更加容易,C1-C2之间以及C3和N(CH₃)的共轭增强效应使得绕C1-C2和C3-N5旋转变得比较困难．这些表明DMAMP初始结构动力学沿着CI-1(S₂/S₀)交叉点展开,而沿CI-2(S₂/S₀)和CI-3(S₂/S₀)交叉点展开的几率可以忽略．提出了DMAMP分子受光激发从S_2,FC(ππ^*)经由各锥形交叉点和各系间窜跃点回到S₀或T_1,min的两个衰变通道.     

2-三氟甲基吡啶的转动光谱及分子结构研究

本文测定了2-三氟甲基吡啶在2∽20 GHz频率范围内的高分辨转动光谱. 测定了转动常数、¹⁴N核四极耦合常数及离心畸变常数等一系列光谱参数. 同时还在自然丰度下测定了5个¹³C和1个¹⁴N单取代同位素异数体的光谱数据. 实验结果结合从头算准确地推导出2-三氟甲基吡啶的骨架结构. 实验测得同位素异数体的平面转动惯量P_cc数值均为44.46 u?²，表明此分子具有C_s对称性. 此外，本文计算了吡啶、2-氟吡啶、2-甲基吡啶和2-三氟甲基吡啶的分子表面静电势，以此分析了三氟甲基的取代对电子分布的影响.     

氰基取代亚甲基自由基的氧气氧化: 新颖Criegee中间体NCC(H)OO顺、反异构体的红外光谱探测

本文采用基质隔离红外光谱分别对15.0 K温度下的HC(N₂)CN/O₂/N₂和HCCNCO/O₂/N₂混合物(1/50/1000)的激光光解过程开展了实验研究. 结果表明：两者在紫外激光光照下均可产生Criegee中间体NCC(H)OO的顺、反两种构象异构体. 对NCC(H)OO的红外光谱解析得到了氧同位素(¹⁸O)标记实验和BP86/6-311++G(3df,3pd)理论计算结果的支持. 实验发现NCC(H)OO在紫外光照下可进一步与氧气分子发生二次反应，生成氰基甲醛和臭氧，而未得到被理论所预测的能量较低的双环氧乙烷异构体cyclic-NCC(O₂)H.     

CuC3H-团簇阴离子与CO反应：H辅助的C-C偶联

本研究利用质谱和密度泛函理论计算研究了CuC₃H^-团簇阴离子与CO的反应. 实验结果指出CO与团簇CuC₃H^-中的C₃H^-部分偶联可生成唯一产物COC₃H^-. 此反应的活性和选择性远高于团簇CuC₃^-与CO的反应. 理论计算结果进一步明确了H辅助的C-C偶联反应.     

A combined experimental and theoretical study on 8-hydroxy-2-quinolinecarboxylic acid

The mid-IR and Raman spectra of 8-hydroxy-2-quinolinecarboxylic acid (8HQC) were recorded. These spectra were interpreted with the help of B3LYP/6–311 ++G(d,p) calculations and potential energy distribution (PED) analysis. As a result of the calculations, seven tautomers were determined among many stable conformations. The experimental spectra were concordant with the theoretical data of one tautomer. In the functional group region overtone and combination bands were detected and assigned. In addition, because of several peaks in the IR spectrum, it was proposed that the 8HQC exhibits dimerization in condensed phase. Possible dimeric forms of 8HQC were evaluated at the same level of theory, and it has been seen that the calculation results confirm the above proposal. ¹H and ¹³C NMR chemical shifts of 8HQC have been calculated, and compared with the experimental data. The frontier molecular orbital properties and the atomic charges were also theoretically obtained and presented.     

Raman spectroscopy of seized drugs and density functional theory interpretation

Abstract

The demand for a hand-held Raman spectrometer in the fast and accurate detection and identification of seized drugs is much higher than before, especially when facing unknown suspicious drugs. However, Raman spectra for the different drugs are less reported due to the inaccessibility of them. Here, we reported the experimental Raman spectra in detail of four typical drugs (such as methamphetamine, ketamine, caffeine, and magu). The Raman vibrational frequencies were also calculated by the method of density functional theory (DFT) at Becke-3-Lee-Yang-Parr (B3LYP) level with the 6-31?G and 6-31G(d,p) basis set. The results show that the experimental Raman spectra of these typical drugs are consistent with the theoretical Raman spectra. Using the potential energy distribution (PED) calculation with the GAR2PED program, the assignments of the observed Raman bands to the vibrational modes were presented. Further, methamphetamine and its camouflage N-benzylisopropylamine were analyzed by Raman spectroscopy and DFT calculations, and the result showed that the obvious differences of the Raman characteristic bands for these two samples could be found so that Raman technique could be used to identify the authenticity of methamphetamine. All the above results confirm the potential of the approach involving Raman spectroscopy combined with DFT calculations in the characterization of drugs. Based on this, the experimental spectra of seized drugs measured directly through a plastic package were studied. Raman spectroscopy has the advantage of being performed through packaging without disturbing the samples. Polypropylene transparent packaging does not alter the spectra of the drugs but will mask the corresponding bands if the Raman spectrum has a strong autofluorescence interference.     

Computational studies of vibrational spectra and molecular properties of 6-methyluracil using HF, DFT and MP2 methods

Theoretical investigations of atomic charges, conformers, frontier molecular orbitals, molecular geometries, thermodynamic properties, hyperpolarizabilities and harmonic vibrational frequencies of 6-methyluracil (6MU) have been carried out using ab initio Hartree-Fock (HF), density functional theory (DFT) and second order M?ller-Plesset (MP2) methods. All calculations were performed using the GAMESS-US program package with the basis sets 6-31G(d,p) and 6-311G(d,p). FT-IR and Raman spectra of 6MU were recorded in the regions 50–4000 cm⁻¹ and 60–4000 cm⁻¹ respectively. Optimized geometries were obtained using the global optimization procedure. The calculated structural parameters for two conformers of 6MU have been compared with experimentally observed values. The energy barrier (ΔE=ELUMO-EHOMO) between the HOMO and LUMO is predicted on the basis of theoretical calculations. The simulated TD-DFT spectrum has been compared with experimental electronic spectrum for 6MU. The calculated potential energy distribution (PED) values have been utilized to perform vibrational assignment of the infrared and Raman spectra.     

Vibrational properties of levulinic acid and furan derivatives: Raman spectroscopy and theoretical calculations

In this work, the Raman spectra of furan, furfuryl alcohol (FA), furfural, hydroxymethylfurfural (HMF), and levulinic acid were obtained in the 500 to 4000 cm⁻¹ spectral region at room temperature. Vibrational wavenumbers were calculated for these compounds with the B3LYP method using the 6‐31 + G(2df,p) basis set. The experimentally determined CC and C C wavenumbers for furan and furan derivatives were in good agreement with the calculated wavenumbers without scaling factor, while the calculated CO and C H wavenumbers at ∼1660 and 3000 cm⁻¹, respectively, showed larger deviations from the measured ones. The Raman spectra for furan and furan derivatives showed intense CC bands, whereas the levulinic acid spectrum showed intense C H vibrations with broad doublet CO bands. We also found that an empirical method based on the chemical structure similarities is able to predict the HMF Raman spectrum from the combined furfural and FA spectra. Copyright © 2011 John Wiley & Sons, Ltd.     

Molecular Dynamics simulations of borate glasses

Abstract

The results of Molecular Dynamics simulations of borate glass (B₂O₃) using three-particle interactions are presented. These calculations yield a glass consisting of randomly connected BO₃ triangles. Infrared and Raman spectra have been calculated and compared with experimental spectra. The calculated infrared spectra show two main bands, one at 650 cm^?1 and one at 1250 cm^?1, in agreement with experiment. The Raman spectra reproduce the experimental peak at 805 cm^?1 but the peak width is a factor of ten too large. Apparently, the simulated glasses have less short range order than the laboratory glasses.     

Vibrational spectroscopic and DFT calculation studies of a new organic–inorganic compound of bis (4-acetylanilinium) tetrachlorocadmiate (II)

The FT-IR and Raman vibrational spectra of bis (4-acetylanilinium) tetrachlorocadmiate (II) compound have been measured at room temperature by FT-infrared spectroscopy (4000–400 cm⁻¹) on polycrystalline samples, and by Raman spectroscopy (3600–30 cm⁻¹) on monocrystals. The structure of the [C₈H₁₀NO] ₂CdCl₄ formed by two cations [C₈H₁₀NO]⁺ of same type and one type of anion [CdCl₄]²⁻ was optimized by density functional theory (DFT) using the B3LYP method. The theoretical wavenumbers spectra were scaled by multiple scaling factors, yielding a good agreement between the experimentally recorded and the theoretically calculated values. Root mean square (rms) value was calculated and the small difference between experimental and calculated modes has been interpreted by intermolecular interactions in the crystal. The comparison between the [C₈H₉NO] ligand and the [C₈H₁₀NO]₂[CdCl₄] compound of the Raman spectra showed a decrease in the wavenumber of the bands assigned to the stretching vibration of (NH₃) group in the compound due to the effect of the protonation of the nitrogen.     

Raman spectrum of decrespignyite [(Y,REE)4Cu(CO3)4Cl(OH)5·2H2O] and its relation with those of other halogenated carbonates including bastnasite,hydroxybastnasite, parisite and northupite

Raman spectroscopy complemented with infrared spectroscopy has been used to study the rare‐earth‐based mineral decrespignyite [(Y,REE)₄Cu(CO₃)₄Cl(OH)₅· 2H₂O] and the spectrum compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of decrespignyite displays three bands at 1056, 1070 and 1088 cm⁻¹ attributed to the CO₃²⁻ symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of the CO₃²⁻ symmetric stretching vibration varies with the mineral composition. The Raman spectrum of decrespignyite shows bands at 1391, 1414, 1489 and 1547 cm⁻¹, whereas the Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm⁻¹, respectively, assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional Raman bands for the ν₃ modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands are observed at 791, 815, 837 and 849 cm⁻¹, which are assigned to the (CO₃)²⁻ν₂ bending modes. Raman bands are observed for decrespignyite at 694, 718 and 746 cm⁻¹ and are assigned to the (CO₃)²⁻ν₄ bending modes. Raman bands are observed for the carbonate ν₄ in‐phase bending modes at 722 cm⁻¹ for bastnasite, 736 and 684 cm⁻¹ for parisite and 714 cm⁻¹ for northupite. Multiple bands are observed in the OH stretching region for decrespignyite, bastnasite and parisite, indicating the presence of water and OH units in the mineral structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Spectroscopy of phonon and vibronic states of YbAl3(BO3)4 single crystal

The polarized Raman and reflection spectra of a single crystal YbAl₃(BO₃)₄ at room temperature were studied. Raman active vibrational modes A ₁, E _TO, and E _LO are identified. In the Raman spectrum, we detected an intense line at a frequency of 1018 cm⁻¹, which refers to internal vibrations of the BO₃ group and is known to be promising for use in amplifiers based on stimulated Raman scattering. From the simulation of reflection spectra by the method of dispersion analysis the frequencies of A ₂ vibrational modes were determined. Intense bands observed in the low-temperature transmission spectra in the range of f-f transitions in the Yb³⁺ ion are attributed to electron-phonon transitions. The Raman lines are compared with electron-phonon lines in the transmission spectrum.     

1,1''联萘-2,2''-二胺拉曼和红外光谱的实验和DFT计算研究

实验测量了1，1''-联萘-2，2''-二胺（BINAM）的红外吸收光谱、可见光激发普通拉曼光谱、紫外共振拉曼光谱.用电子密度泛函方法计算了BINAM的基态几何构型、振动频率、普通拉曼和近共振拉曼强度.通过实验和理论计算对比，对所得红外和拉曼提出了详细的指认，并且分析了各振动模式的特征.BINAM的紫外共振拉曼光谱与普通拉曼光谱相比较，发现有若干拉曼谱带出现了选择性共振增强.基于共振拉曼强度分析，讨论了BINAM可能的激发态几何结构的变形.     

First principles analysis of the MgAl2O4:Ni absorption spectrum

Analysis of the energy-level scheme and absorption spectrum of the Ni²⁺ ion in MgAl₂O₄ was performed. The recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multi-electron (DV-ME) method [K. Ogasawara, et al., Phys. Rev. B 64 (2001) 115413) was used in the calculations. The method is based on the numerical solution of the Dirac equation; no phenomenological parameters are used in the calculations. As a result, complete energy-level scheme of Ni²⁺ and its absorption spectra were calculated, assigned and compared with experimental data on the ground and excited state absorption spectra. Numerical contributions of all possible electron configurations into the calculated energy states were determined. By performing analysis of the molecular orbitals population, numerical contributions of the oxygen 2p- and 2s-orbitals into the 3d molecular orbitals were determined.