Calculations on polarization properties of alkali metal atoms using Dirac–Fock plus core polarization method

A semi-empirical atomic structure model method is developed in the framework of a relativistic case. This method starts from Dirac-Fock calculations using B-spline basis set. The core-valence electron correction is then treated in a semiempirical core polarization potential. As an application, the polarization properties of alkali metal atoms, including the static polarizabilities and long-range two-body dispersion coefficients, have been calculated. Our results are in good agreement with the results obtained from ab initio relativistic many-body perturbation method and the available experimental measurements.     

有没有搞错

在四则运算中,简算给我们带来了方便,但有的同学太懒,聪明反被聪明误,弄巧成拙,闹出一些笑话。当看到作业本上又大又红的叉叉时,他会来一句"有没有搞错",那到底有没有搞错呢?我们一起来看看吧!不公平这位同学知道凑整的简便方法,但是却没有给1分配。为了使等式成立,这里应该给100-1加括号,然后用乘法分配律,多算了一个28当然就要减去一个28。     

三环已基锡R-扁桃酸酯配合物的合成、结构及性质研究

三环己基氢氧化锡与R-扁桃酸按物质的量比1:1在苯溶剂中反应合成了三环己基锡R-扁桃酸酯。经X-射线衍射方法测定了其晶体结构, 配合物属斜方晶系, 空间群为P2₁2₁2₁2₁, 晶体学参数a=0.806 41(4) nm, b=1.768 68(9) nm, c=1.834 79(8) nm, V=2.616 9(2) nm³, Z=4, D_c=1.318 g·cm^-3, (Mo Ka)=9.98 cm^-1, F(000)=1 080, R₁=0.039 0, wR₂=0.103 9。中心锡原子与环己基碳原子和氧原子构成畸型四面体。对其结构进行量子化学从头计算, 探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。研究了配合物的热稳定性、荧光性质和电化学性能。     

Quasi-classical Trajectory Study of F-I-H20→HF-I-OH Reaction： Influence of Barrier Height,Reactant Rotational Excitation,and Isotopic Substitution

The reaction dynamics of the F＋H20/D20→HF/DF＋OH/OD are investigated on an accurate potential energy surface （PES） using a quasi-classical trajectory method. For both isotopomers, the hydrogen/deuterium abstraction reaction is dominated by a direct rebound mechanism over a very low ＂reactant-like＂ barrier, which leads to a vibrationally hot HF/DF product with an internally cold OH/OD companion. It is shown that the lowered reaction barrier on this PES, as suggested by high-level ab initio calculations, leads to a much better agreement with the experimental reaction cross section, but has little impact on the product state distributions and mode selectivity. Our results further indicate that rotational excitation of the H20 reactant leads to significant enhancement of the reactivity, suggesting a strong coupling with the reaction coordinate.     

OCl2分子基态势能曲线的从头算研究

采用三重激发耦合族理论(CCSD),使用多种基组对OCl2分子基态结构进行几何优化,选出最优基组6-311G(2df)对OCl2分子的离解能、谐振频率和力常数等进行了计算,其结果与实验值符合很好.在此基础上推导出OCl2分子基态的多体展式势能函数,其等值势能曲线正确反应了OCl2分子的结构特征及势阱深度,进一步讨论了Cl+OCl和O+ClCl分子反应的势能面特征.这些结果可用于微观反应动力学的研究.     

振动频率与芳香分子稳定性的判定

通过使用7个从头计算方法、7个密度泛函理论(DFT)方法和20个常用基组对66个苯、萘、蒽、联二亚苯、苊及其衍生物计算振动频率后发现只有10个分子完全不出现虚频,而且共有1365个方法/基组出现虚频;其中7个DFT方法,HF方法和MP2方法所出现的虚频数占各自总的计算方法/基组数的比例分别为7.01%,7.34%和36.38%.除mPW2PLYPD以外的所有方法计算含甲基或铵基的16个分子的结果都非常不可靠,但DFT和HF方法对除此类分子以外的其它芳香分子从计算所出现虚频的比例可以被忽略的角度来看都显得相当可靠.当45个杂环芳香化合物及其衍生物被类似地计算时,DFT方法,HF方法和MP2方法所出现的虚频比例分别为2.11%,2.78%和27.44%.不但用苯的实验结构进行计算不能消除虚频,而且用苯和甲苯的平面或非平面优化结构计算也都不能消除虚频;同时用一百多个方法和一百多个基组计算苯和甲苯时,出现的虚频比例更高达18.18%.这些均说明从头计算方法和DFT方法计算频率有不可靠或不适用的地方,并且那种认为苯和其它芳烃为非平面结构的观点至少不能说是完全正确的.     

RDX分子内振动能量重分配的动力学研究

基于从头算分子动力学(Born-oppenheimer molecular dynamics, BOMD)模拟, 构建了环硝胺六氢-1,3,5-三硝基-1,3,5-三嗪(RDX)单分子不同振动模式之间的耦合矩阵, 并计算了在不同加载能量下从低频振动模式到高频振动模式的最优能量传输路径. 结果表明, RDX单分子中—NNO₂基团更有利于能量局域化, 振动模式v₃和v₄在从低频振动模式到高频振动模式的能量传输过程中扮演着重要角色. 通过对v₃和v₄两个振动模式的进一步分析发现, 加载能量的不同会导致RDX单分子能量传输路径的不同. 当加载能量较低时, RDX单分子倾向于从低频振动模式到中频振动模式再到高频振动模式的能量传输路径; 当加载能量较高时, 能量更倾向于从低频振动模式直接传输到高频振动模式上. 揭示了RDX分子内振动耦合能量转移的微观机制, 为进一步探索RDX将“机械能”转化为“化学能”的微观过程提供了理论基础.     

Ab initio calculations on the spectroscopic constants, vibrational levels and classical turning points for the 21∏u state of dimer 7Li2

The accurate dissociation energy and harmonic frequency for the highly excited 2^1Пu state of dimer ^7Li2 have been calculated using a symmetry-adapted-cluster configuration-interaction method in complete active space. The calculated results are in excellent agreement with experimental measurements. The potential energy curves at numerous basis sets for this state are obtained over a wide internuclear separation range from about 2.4a0 to 37.0a0. And the conclusion is gained that the basis set 6-311＋＋G（d,p） is a most suitable one. The calculated spectroscopic constants De, Re, ωe, ωeχe, ae and Be at 6-311＋＋G（d,p） are 0.9670 eV, 0.3125 nm, 238.6 cm^-1, 1.3705 cm^-1, 0.0039 cm^-1 and 0.4921 cm^-1, respectively. The vibrational levels are calculated by solving the radial SchrSdinger equation of nuclear motion. A total of 53 vibrational levels are found and reported for the first time. The classical turning points have been computed. Comparing with the measurements, in which only the first nine vibrational levels have been obtained so far, the present calculations are very encouraging. A careful comparison of the present results of the parameters De and We with those obtained from previous theories clearly shows that the present calculations are much closer to the measurements than previous theoretical results, thus representing an improvement on the accuracy of the ab initio calculations of the potentials for this state.     

NMR Parameters and Vibrational Investigation of 2-Dicyanovinyl-5-（4-ethoxyphenyl） thiophene by ab initio HF and DFT Calculations

Optimized geometry and harmonic vibrational frequency of 2-dicyanovinyl-5-(4- ethoxyphenyl)thiophene (C16H12N2OS) are calculated at the HF/6-31++G(d,p) and B3LYP/6- 311++G(d,p) levels. Mulliken charges in the ground state are also calculated. The research shows the presence of intermolecular interaction in the title compound. The scaled harmonic vibrational frequencies have been compared with experimental FT-IR spectra. A detailed interpretation of the infrared spectra of the title compound is reported. The theoretical spectrograms for IR spectra of the title compound have been constructed. The isotropic chemical shift computed by 13C and 1H NMR analyses also shows good agreement with the experimental observations.     

Wn(n=3—27)原子团簇结构的第一性原理计算

使用密度泛函理论下的第一性原理方法，对W_n原子团簇(n=3—27)的结构特性进行了理论计算. 得到了W_n团簇(n=3—7)的最低能量结构和(n=8—27)的局域能量极小的典型结构. 使用凝胶模型，提出的电子组态1s²1p⁶1d¹⁰2s²1f¹⁴2p⁶3s