咖啡酸分子振动光谱的理论研究

本文采用DFT方法(B3LYP)研究了咖啡酸分子的平衡几何构型和振动光谱。在B3LYP水平上,以6-311++G**为基组计算了其平衡构型下的谐振动力场"振动频率和振动强度。使用Wilson的GF矩阵方法对其进行了简正坐标分析,依据所得的势能分布(PEDs)对咖啡酸分子的振动基频进行了合理的理论归属。     

槲皮素分子结构和振动光谱的理论研究

本文采用密度泛函理论(DFT)方法研究了槲皮素分子的平衡几何构型和振动光谱。在B3LYP水平上,以6-311++G**为基组计算了其平衡构型下的谐振动力场﹑振动频率和振动强度。使用Wilson的GF矩阵方法对其进行了简正坐标分析,依据所得的势能分布(PEDs)对槲皮素分子的振动基频进行了合理的理论归属。     

3,4-二硫方酸芳香性和气相酸性的理论研究

在RHF/6-311G^**,RHF/6-311+G^**和B3LYP/6-311+G^**水平优化得到3,4-二硫方酸(3,4-二巯基-3-环丁烯-1,2-二酮)三种平面构象异构体的平衡几何构型.用MP2(Full)/6-311G^**//RHF/6-311G^**方法计算单点能量,发现ZZ型异构体是能量最低构象,且ZZ和ZE型能量非常接近.用优化的最稳定构象ZZ型异构体在RHF/6-311G^**//RHF/6-311G^**,RHF/6-311G^**//RHF/6-311G^**,MP2(Full)/6-311G^**//RHF/6-311G^**和B3LYP/6-311G^**//B3LYP/6-311G^**水平计算其气相酸性(ΔG⁰)和同键反应芳香性稳定化能(HASE).用基团加和法(Group Increment Approach)在RHF/6-311G^**//RHF/6-311G^**和B3LYP/6-311G^**//B3LYP/6-311G^**水平计算其磁化率增量(Λ).计算结果表明,标题化合物的同键反应芳香性稳定化能和磁化率增量均为负值,表明它具有芳香性,实现了标题化合物芳香性的几何、能量和磁性的判定.     

乙烯、乙炔和苯与氨基锂间的π型锂键相互作用

分别在DFT-B3LYP和MP2/6-311++G**水平上求得乙烯、乙炔和苯与氨基锂锂键复合物势能面上的3个几何构型. 频率分析表明,3个构型均为稳定构型. 计算结果表明,形成锂键复合物后,质子供体N(2)- Li(4)的键长明显增大,且其伸缩振动的频率发生了不同程度的红移. 分别在乙烯…氨基锂、乙炔…氨基锂和苯…氨基锂三种复合物中,经MP2/6-311++G**水平计算的同时含基组重叠误差(BSSE)和零点振动能校正的单体间锂键相互作用能分别为-26.04、-24.86 和 -30.02 kJ·mol-1. 自然键轨道理论（NBO）分析表明单体间的弱相互作用属于π-s型锂键.     

气相中O3与HSO自由基间的氢键复合物

气相中O3与HSO自由基之间的相互作用及其反应在大气化学中非常重要. 在DFT-B3LYP/6-311++G**和MP2/6-311++G**水平上求得O3+HSO复合物势能面上的稳定构型, B3LYP方法得到了三种构型(复合物I, II和III), 而MP2方法只能得到一种构型(复合物II). 在复合物I和III中, HSO单元中的1H原子作为质子供体, 与O3分子中的端基O原子作为质子受体相互作用, 形成红移氢键复合物; 而在复合物II中, 虽与复合物I和III中具有相同的质子供体和质子受体, 却形成了蓝移氢键复合物. B3LYP/6-311++G**水平上计算的单体间相互作用能的计算考虑了基组重叠误差(BSSE)和零点振动能(ZPVE)校正, 其值在-3.37到-4.55 kJ·mol-1之间. 采用自然键轨道理论(NBO)对单体间相互作用的本质进行了考查, 并通过分子中原子理论(AIM)分析了三种复合物中氢键的电子密度拓扑性质.     

BrONO2光解反应的理论研究

采用密度泛函方法,研究了大气臭氧层主要破坏物BrONO2的光解反应机理,在UB3LYP/6-311++G**水平上优化了反应物、产物、中间体和过渡态的几何构型,并在UQCISD(T)/6-311++G**水平上计算了单点能量,为了确证过渡态的真实性,在UB3LYP/6-311++G**水平上进行了内禀反应坐标(IRC)计算和频率分析.研究结果表明,BrONO2的光解反应有两条反应通道,其中生成BrO+NO2的反应活化能较小(14.89 kJ·mol-1),较易发生.     

气相中O3与HSO自由基间的氢键复合物

气相中O3与HSO自由基之间的相互作用及其反应在大气化学中非常重要.在DFT-B3LYP/6-311++G**和MP2/6-311++G**水平上求得O3+HSO复合物势能面上的稳定构型,B3LYP方法得到了三种构型(复合物Ⅰ,Ⅱ和Ⅲ),而MP2方法只能得到一种构犁(复合物Ⅱ).在复合物Ⅰ和Ⅲ中,HSO单元中的1H原子作为质子供体.与O3分子中的端基O原子作为质子受体相互作用,形成红移氢键复合物;而在复合物Ⅱ中,虽与复合物Ⅰ和Ⅲ中具有相间的质子供体和质子受体,却形成了蓝移氢键复合物.B3LYP/6-311++G**水平上计算的单体间相互作用能的计算考虑了基组重甍误差(BSSE)和零点振动能(ZPVE)校正,其值在-3.37到-4.55 kJ·mol-1之间.采用自然键轨道理论(NBO)对单体间相互作用的本质进行了考查,并通过分子中原子理论(AIM)分析了三种复合物中氢键的电子密度拓扑性质.     

硅炔氢加成生成甲硅烷基硅烯的量子化学研究

利用量子化学从头算和密度泛函理论(DFT), 研究了硅炔和氢气分子加成生成甲硅烷基硅烯的反应机理. 在B3LYP/6-311G**水平上, 全参数优化了反应通道上各驻点(反应物、过渡态和产物)的几何构型, 计算出了它们的振动频率和零点振动能(ZPVE), 并对它们进行了振动分析, 以确定过渡态的真实性. 各物质总能量由QCISD(T)/6-311G**// B3LYP/6-311G**给出, 并对能量进行了零点能校正. 计算表明, 硅炔与氢分子加成反应可生成稳定的甲硅烷基硅烯. 热力学与动力学计算表明, 反应过程是一个放热、熵减少而自发趋势和反应程度较大的反应.     

线型碳链PC2nP的结构和电子光谱的密度泛函理论研究

应用密度泛函理论,在B3LYP/6-31G**和B3LYP/6-311G**水平上优化得到了线型簇合物PC2nP(n=1-10)的基态平衡几何构型,计算了它们的谐振动频率.在基态平衡构型下,利用含时密度泛函理论,计算得到了簇合物PC2nP(n=1-10)的垂直激发能和相应的振子强度,导出了激发能与体系大小n的解析关系式.     

阿魏酸分子结构和振动光谱的理论研究

阿魏酸是一种有效的天然油脂抗氧化剂.采用密度泛函理论(DFT) B3LYP方法和从头算HF两种方法,在6-311++G**基组水平上对阿魏酸分子的几何结构进行全优化,得到其几何结构参数,进一步计算得到阿魏酸的红外和拉曼振动光谱.计算结果表明,采用B3LYP和HF 2种方法优化得到的几何结构及频率值是一致的,对在B3LYP方法下计算得到的红外和拉曼振动频率进行合理的理论归属并与SDBS数据库实验数据进行比较,发现计算得到的红外和拉曼振动频率与实验测定结果符合较好.阿魏酸分子结构和振动光谱的研究,为研究阿魏酸及其衍生物的化学结构与生理活性之间的构效关系提供依据.     

Ab-initio and density functional study of L- and D-forms of alanine and serine in gas phase and bulk aqueous medium

The molecular geometry of L and D-forms of alanine and serine in gas phase have been studied by using ab-initio quantum chemical calculations at the restricted Hartree-Fock (RHF) level by employing 6-31G and 6-311++G** basis sets. Subsequently, for considering the electron correlations, Density functional Calculations at the Becke3LYP (B3LYP) and Moller-Plesset second order (MP2) level of calculations have been carried out with the same basis sets for these optimized geometries. Effect of solvation in water on the optimized geometries was studied using the polarized continuum model of the self-consistent reaction field (SCRF) theory. The dipole moment, energy, polarizabilities and vibrational frequencies have been calculated in all cases. Frequency analysis was carried out to ensure that optimized geometry corresponds to a total energy minimum.     

Theoretical investigation of the structure and vibrational spectra of carbamoyl azide

Molecular structure and vibrational frequencies of carbamoyl azide NH2CO-NNN have been investigated with ab initio and density functional theory (DFT) methods. The molecular geometries for all the possible conformers of the molecule were optimized using DFT-B3LYP, DFT-BLYP and MP2 applying the standard 6-311++G** basis set. From the calculations, the molecule was predicted to exist predominantly in cis conformation with the cis-trans rotational barrier of about 7.91-9.10 kcal/mol depending on the level of theory applied. The vibrational frequencies and the corresponding vibrational assignments of carbamoyl azide in Cs symmetry were examined theoretically and the calculated Infrared and Raman spectra of the molecule in the cis conformation were plotted. Observed frequencies for normal modes were compare with those calculated from normal mode coordinate analysis carried out on the basis of ab initio and DFT force fields using the standard 6-311++G** basis set of the theoretical optimized geometry. Theoretical IR intensities and Raman activities are reported.     

Theoretical study of light-metal tetrahydroborates

Ab initio calculations of the structural, energetic, vibrational, and magnetic characteristics of the lowest-lying structures for isolated molecules and ions of light-metal tetrahydroborates (Li, Na, Be, Mg, and Al) have been performed by the perturbation theory (MP2), quadratic configuration interaction (QCISD(T)), coupled cluster (CCSD(T)), and density functional theory (B3LYP) methods using the 6-31G*, 6-31G**, 6-311+G**, and 6-311++G** basis sets. The trends in the behavior of the structural parameters, the energies of different decomposition pathways, barriers to internal rotation of BH₄ groups, normal mode frequencies, magnetic shielding constants, and spin density distribution (in radicals) have been analyzed in various related series of these compounds. The results obtained by ab initio methods and at the DFT level are compared. The economical approximation B3LYP/6-311++G**//B3LYP/6-311+G** adequately reproduces the results obtained at the higher level of theory CCSD(T)/6-311++G*s*//MP2/6-31G* even though it requires considerably shorter CPU times and smaller amounts of memory.     

Theoretical study of light-metal tetrahydroaluminates

Ab initio calculations of the structural, energetic, vibrational, and magnetic characteristics of the lowest-lying structures for isolated molecules and ions of light-metal tetrahydroaluminates (Li, Na, Be, Mg, and Al) have been performed by the perturbation theory (MP2), quadratic configuration interaction (QCISD(T)), coupled cluster (CCSD(T)), and density functional theory (B3LYP) methods using the 6-31G*, 6-31G**, 6-311+G**, and 6-311++G** basis sets. The trends in the behavior of the molecular characteristics have been analyzed in various related series of these compounds. The results are compared with the data on analogous light-metal tetrahydroborates calculated at the same levels of theory. The differences in structure and stability between analogous hydroborate and alanate complexes are examined. The economical approximation B3LYP/6-311++G**//B3LYP/6-311+G** has been shown to adequately reproduce the results obtained at the higher level of theory CCSD(T)/6-311++G**//MP2/6-31G* even though it requires considerably shorter CPU times and smaller amounts of memory.     

Three rotor potential energy scans, conformational equilibrium constants and vibrational analysis of 3-fluoro-1-propanol CH(2)FCH(2)CH(2)OH

The conformational stability and the three rotor internal rotations in 3-fluoro-1-propanol were investigated by the DFT-B3LYP/6-311+G** and the ab initio MP2/6-311+G** levels of theory. The calculated potential energy curves of the molecule at both levels of theory were consistent with complex conformational equilibria of about 12 minima, all of which were predicted to have real frequencies at both the B3LYP and the MP2 levels. The lowest energy minimum in the potential curves of 3-fluoro-1-propanol was predicted to correspond to the Gauche-gauche-trans (Ggt) conformer in excellent agreement with microwave and electron diffraction results. The equilibrium constants for the conformational interconversion of the molecule were calculated and found to correspond to an equilibrium mixture of about 33% Ggt, 14% Ggg1 and 13% Gg1g and about 43% Ggt, 12% Ggg1 and 10% Gg1g distribution by the B3LYP/6-311+G** and the MP2/6-311+G** calculations, respectively, at 298.15K. The vibrational frequencies of each molecule in its three stable forms were computed at B3LYP level and complete vibrational assignments were made based on normal coordinate calculations and comparison with experimental data of the molecule.     

Ab initio studies of aspartic acid conformers in gas phase and in solution

Systematic and extensive conformational searches of aspartic acid in gas phase and in solution have been performed. For the gaseous aspartic acid, a total of 1296 trial canonical structures and 216 trial zwitterionic structures were generated by allowing for all combinations of internal single-bond rotamers. All the trial structures were optimized at the B3LYP/6-311G* level and then subjected to further optimization at the B3LYP/6-311++G** level. A total of 139 canonical conformers were found, but no stable zwitterionic structure was found. The rotational constants, dipole moments, zero-point vibrational energies, harmonic frequencies, and vertical ionization energies of the canonical conformers were determined. Single-point energies were also calculated at the MP2/6-311++G** and CCSD/6-311++G** levels. The equilibrium distributions of the gaseous conformers at various temperatures were calculated. The proton affinity and gas phase basicity were calculated and the results are in excellent agreement with the experiments. The conformations in the solution were studied with different solvation models. The 216 trial zwitterionic structures were first optimized at the B3LYP/6-311G* level using the Onsager self-consistent reaction field model (SCRF) and then optimized at the B3LYP/6-311++G** level using the conductorlike polarized continuum model (CPCM) SCRF theory. A total of 22 zwitterions conformers were found. The gaseous canonical conformers were combined with the CPCM model and optimized at the B3LYP/6-311++G** level. The solvated zwitterionic and canonical structures were further examined by the discrete/SCRF model with one and two water molecules. The incremental solvation of the canonical and zwitterionic structures with up to six water molecules in gas phase was systematically examined. The studies show that combining aspartic acid with at least six water molecules in the gas phase or two water molecules and a SCRF solution model is required to provide qualitatively correct results in the solution.     

Density functional theory study on the structure and vibrational frequencies of glycylglycine

Eleven possible conformers of glycylglycine have been studied by using the BLYP, B3LYP methods of density functional theory and the HF method at the basis set of 6-311++G**. BLYP (using Becke's and Lee-Yang-Parr's correlation functionals), ab initio Hartree-Fock (HF) and hybrid DFT/HF B3LYP calculations have been carried out to study the structure and vibrational spectra of glycylglycine. Glycylglycine crystal structure has been determined by X-ray diffraction analysis. The title compound has been crystallizes in the orthorhombic space group C1, with Z=4. And the unit cell parameters are: a=8.1184(12)A, b=9.5542(14)A, c=7.8192(11)A and V=577.95(15)A(3). Molecular conformation calculations have got 11 possible conformers. In these possible conformers, the most stable one has been selected. The BLYP/6-311++G** and scaled HF/6-311++G** frequencies correspond well with available experimental assignments of the normal vibrational modes. Comparison of the observed fundamental vibrational frequencies of glycylglycine and calculated results by density functional B3LYP and Hartree-Fock (HF) methods indicates that B3LYP is superior to the scaled Hartree-Fock (HF) for molecular vibrational issues.     

A study of internal rotations and vibrational spectra of oxiranemethanol (glycidol)

The conformational stability and the C–O and O–H internal rotations in oxiranemethanol were investigated at the DFT-B3LYP/6-311G**, MP2/6-311G** and MP4(SDQ)/6-311G** levels of theory. Three minima were predicted in the CCOH potential energy scans of the molecule to have relative energies of about 2 kcal/mol or less and all were calculated to have real frequencies upon full optimization of structural parameters at the DFT and the MP2 levels of calculations. The Cg1 (H bond inner) conformation was predicted to be the lowest energy conformation for oxiranemethanol in excellent agreement with an earlier microwave study. The equilibrium mixture was calculated from Gibb's free-energy changes to be about 79% Cg1, 17% G1g and 3% Gg1 at the B3LYP/6-311G** level and about 87% Cg1, 11% G1g and 2% Gg1 at the MP2/6-311G** level for oxiranemethanol at 298.15 K. No conclusive evidence was obtained for the presence of high-energy form in the liquid phase of oxiranemethanol. The vibrational frequencies of oxiranemethanol in its three stable forms were computed at the B3LYP level and complete vibrational assignments were made for the lowest energy Cg1 form on basis of calculated and experimental data of the molecule.