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 .     

合成气在Rh（111）上转化为乙醇的机理的键级守恒研究

Rh上乙醇的生成机理,目前主要有两类.一是Ichikawa等为代表提出的“CO解离—CH_x(x=2或3)—乙酰基—乙醇”机理;另一是蔡启瑞等的“CO缔合—甲酰基(金属氧卡宾)—卡宾—乙烯酮—乙酰基—乙醇”机理.本文用Shustorovich的键级守恒—Morse势(BOC-MP)法对其进行了研究     

Localized molecular orbitals and the problem of quasi-aromaticity in trinuclear molybdenum cluster compounds with cores of the type [MO3(μ3-X)(μ-Y)3] (X, Y = O, S, n = 4; X = O, Y = Cl, n = 5)

Calculations of localized molecular orbitals (LMO) and their energy levels for the cluster cores [MO₃O₄]⁴⁺, [MO₃SO₃]⁴⁺, [MO₃OS₃]⁴⁺, [Mo₃S₄]⁴⁺ and [MO₃OCl₃]⁵⁺ have been made by the use of energy-localized CNDO/2-LMO. The results of these LMO calculations show that the six-membered closed and continuous π-conjugated systems around the [MO₃Y₃] rings, each of which is formed from three synergically connected three-centered two-electron π bonds, is the most significant feature of the electronic structure for the quasi-aromatic clusters [Mo₃(μ₃-Y)(μ-X)₃]⁴⁺ (X, Y = O, S), and the size and electronegativity of the bridging Y atoms exhibit significant effects on the degree of quasi-aromaticity of these cluster compounds. For the non-aromatic reference cluster [Mo₃OCl₃]⁵⁺, the results of our calculations also show a bonding scheme with only one isolated π bond, thus leading to the loss of quasi-aromaticity; and meanwhile, there is a pair of extra electrons localized on the apical molybdenum atom of the Mo₃ triangle, thus with three Mo---Mo single bonds.     

Valence bond theoretical study for chemical reactivity

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Organic functionalization of the sidewalls of carbon nanotubes by diels-alder reactions: a theoretical prediction

[structure: see text] The viability of the Diels-Alder (DA) cycloaddition of conjugated dienes onto the sidewalls of single-wall carbon nanotubes is assessed by means of a two-layered ONIOM(B3LYP/6-31G:AM1) approach. Whereas the DA reaction of 1,3-butadiene on the sidewall of an armchair (5,5) nanotube is found to be unfavorable, the cycloaddition of quinodimethane is predicted to be viable due to the aromaticity stabilization at the corresponding transition states and products.     

Hyperpolarizabilities of Chelidamic Acid Complexes M_m(C_7H_3O_5N)_n (M=Cu, Ag): Theoretical Analysis

The frequency‐dependent hyperpolarizabilities of chelidamic acid complexes M_m(C₇H₃O₅N)_n (M?Cu, Ag) were investigated under the time dependent density functional theory (TDDFT) combined with the sum‐over‐states method (SOS). The relationship between molecular orbitals and nonlinear optical (NLO) properties has been explored. The results show that the charge transitions of π‐π* and 3d_M‐π* are very important to the second‐order polarizabilities, and the largest component of dynamic β is 3.84×10^?25 cm⁵·esu^?1 at 0.74 eV for Ag₂Cu₂(C₇H₃O₅N)₄. The charge transition between π‐π* is also highly crucial to the third‐order polarizabilities, and the largest component of dynamic γ is ?4.46×10^?29 esu at 0.50 eV for Ag₂Cu₂(C₇H₃O₅N)₄. The central Cu ion, as electron bridge, extends the range of delocalization and leads to an interesting phenomenon of spiroconjugation.     

Ab Initio Study on The Influence of Spin State upon Bonding and Interaction in Fe-COBondCovalenciesinR2BaCuO5(R=Sm,Gd,Dy,Ho,Y,Er,Tm,Yb,Lu)

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Orbital deletion procedure and its applications

The orbital deletion procedure is introduced, which is suited to quantitatively investigating the electronic delocalization effiect in earboeations and boranes. While the routine, ab initio molecular orbital methods can generate wavefunetions for real systems where all electrons are delocalized, the present orbital deletion procedure can generate wavefunctions for hypothetical reference molecules where electronic delocalization effect is deactivated. The latter wavefunetion normlly corresponds In the most stable resonance structure in terms of the resonance theory. By comparing and analyzing the delocalized and the localized wavefunetions, one can obtain a quantitative and instinct pieture to show how electronic deloealizalion inside a molecule affects the molecular structure, energy as well as other physical properties. Two examples are detailedly discussed. The first is related to the hypercoujugation of alkyl groups in carbocations and a comparison of the order of stability of carbocations is made, T