Systematic formulations for electronegativity and hardness and their atomic scales within density functional softness theory

A unified Mulliken valence with Parr ground‐state electronegativity picture is presented. It provides a useful analytical tool on which the absolute hardness as well ionization potential and electron affinity functionals are based. For all these chemical reactivity indices, systematic approximate density functionals are formulated within density functional softness theory and are applied to atomic systems. For the absolute hardness, a special relationship with the new electronegativity ansatz and a particular atomic trend paralleling the absolute electron affinity are established that should complement and augment the earlier finite‐difference energetic approach. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Electronic structure and vibrational spectra of cis-diammine(orotato)platinum(II), a potential cisplatin analogue: DFT and experimental study

Orotic acid (vitamin B₁₃) is a key intermediate in biosynthesis of the pyrimidine nucleotides in living organisms, moreover, it may serve as the biological carrier for some metal ions. cis-Diammine(orotato)platinum(II), cis-[Pt(C₅H₂N₂O₄)(NH₃)₂] can be considered as a new potential cisplatin analogue. The FT-Raman and FT-IR spectra of the title complex are reported, for the first time. The molecular structure, vibrational frequencies, and the theoretical infrared and Raman intensities have been calculated by the density functional mPW1PW91 method. The detailed vibrational assignment has been made on the basis of the calculated potential energy distribution. The theoretically predicted IR and Raman spectra show very good agreement with experiment. Natural bond orbital (NBO) analyses were performed for cisplatin, carboplatin and the title complex. The results provided new data on the nature of platinum–ligand bonding in these compounds. Strong intramolecular hydrogen bond between the orotate ligand and the coordinated ammonia group stabilizes the structure of the platinum(II) complex. Thus, it is suggested that the orotate ligand in the title complex is more inert to the substitution reactions than the chloride ligands in cisplatin.     

小分子硫原子团簇正离子的结构稳定性

用分子图形软件设计出 4 9种硫原子团簇Sn+ (n =3～ 13)的结构 ,使用B3LYP密度泛函进行几何构型优化和振动频率计算 ,根据分子的总能量得出最稳定的同分异构体 .在硫原子团簇正离子中 ,大部分原子为二配位成键 .带有一、三配位的原子结构的总能量较高 .部分最稳定硫原子团簇正离子的构型与最稳定的中性硫原子团簇的构型完全不同 .     

Surface rumpling of cubic CaTiO3 from density functional theory

In this paper, the structure of cubic CaTiO3 （001） surfaces with CaO and TiO2 terminations has been studied from density functional calculations. It has been found that the Ca atom has the largest relaxation for both kinds of terminations, and the rumpling of the CaO-terminated surface is much larger than that of TiO2-terminated surface. Also we have found that the metal atom relaxes much more prominently than the O atom does in each layer. The CaO-terminated surface is slightly more energetically favourahle than the TiO2-terminated surface from the analysis of the calculated surface energy.     

Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.     

非对称三态叠加多模泛函叠加态光场的高次压缩——广义电场分量的不等幂次和压缩效应研究

多模真空态|{0j}〉q与两个空间强度分布特征不同的多模复共轭泛函相干态|{f(j a)*(x,y,z)}〉q和|{f(j b)*(x,y,z)}〉q的线性叠加组成的三态叠加多模泛函叠加态光场|ψ(f3)〉q,利用多模压缩态理论,研究了态|ψ(f3)〉q中广义电场分量的不等幂次高次和(H)压缩特性.结果表明:在一定的条件下,态|ψ(f3)〉q的广义电场分量可呈现出周期性变化的任意奇数次和任意偶数次的不等幂次高次H压缩效应;光场的经典振幅和经典初始相位的任意非对称空间分布特征对其压缩程度和压缩深度等压缩特性将产生直接的影响.     

A Model for Spacetime: The Role of Interpretation in Some Grothendieck Topoi

We analyse the proposition that the spacetime structure is modified at short distances or at high energies due to weakening of classical logic. The logic assigned to the regions of spacetime is intuitionistic logic of some topoi. Several cases of special topoi are considered. The quantum mechanical effects can be generated by such semi-classical spacetimes. The issues of: background independence and general relativity covariance, field theoretic renormalization of divergent expressions, the existence and definition of path integral measures, are briefly discussed in the proposal. The connection with some problems in foundations of mathematics and differential topology are also discussed.     

Converged properties of clean metal surfaces by all-electron first-principles calculations

All-electron full-potential linearized augmented plane-wave calculations of the surface energy, work function, and interlayer spacings of close-packed metal surfaces are presented, in particular, for the free-electron-like metal surfaces, Mg(0 0 0 1) and Al(1 1 1), and for the transition metal surfaces, Ti(0 0 0 1), Cu(1 1 1), Pd(1 1 1), and Pt(1 1 1). We investigate the convergence of the surface energy as a function of the number of layers in the slab, using the Cu(1 1 1) surface as an example. The results show that the surface energy, as obtained using total energies of the slab and bulk from separate calculations, converges well with respect to the number of layers in the slab. Obviously, it is necessary that bulk and surface calculations are performed with the same high accuracy. Furthermore, we discuss the performance of the local-density and generalized gradient approximations for the exchange-correlation functional in describing the various surface properties.     

Density functional theory investigation of the structure of SO2 and SO3 on Cu(1 1 1) and Ni(1 1 1)

Density functional theory (DFT) slab calculations, mainly using the generalised gradient approximation, have been used to investigate the minimum energy structures of molecular SO₂ and SO₃ on Cu(1 1 1) and Ni(1 1 1) surfaces. On Ni(1 1 1) the optimal local adsorption structures are in close agreement with experimental results for both molecular species obtained using the X-ray standing wavefield technique, although for adsorbed SO₂ the energetic difference between two alternative lateral positions of the lying-down molecule on the surface is marginally significant. On Cu(1 1 1) the results for adsorbed SO₂, in particular, were sensitive to the DFT functional used in the calculations, but in all cases failed to reproduce the experimentally-established preference for adsorption with the molecular plane perpendicular to the surface. This result is discussed in the context of previously published DFT results for these species adsorbed on Cu(1 0 0). The optimal geometry found for SO₃ on Cu(1 1 1) is similar to that on Ni(1 1 1), providing agreement with experiment regarding the molecular orientation but not the adsorption site.     

VOn±(n=0,1,2)的势能函数与光谱常数研究

用密度泛函B3LYP/6-311++G(d,p)方法和相对论有效实势(Lanl2dz基组)对VO^n±(n=0,1,2)分子离子的势能函数及光谱常数进行了分析. 结果表明它们都能稳定存在, 其基态电子状态分别是:⁴Σ(VO^2-), ³Σ(VO^-), ⁴Σ(VO), ³Σ(VO⁺)和²Σ(VO²⁺). 其中VO^2-和VO²⁺的势能函数曲线呈“火山口”型, 属于亚稳态分子离子. 用七参数Murell-Sorbie势拟合VO^2-和VO²⁺分子亚稳态双原子分子离子势能函数, 发现其拟合曲线与势能函数曲线符合得很好. 同时,讨论了电荷对势能函数和能级的影响. 关键词： 分子离子 密度泛函理论 势能函数 能级