紫外吸收温差光谱法及其应用

用温差光谱法观察系列化合物的紫外吸收温差谱，发现温差谱具有很强的特征性，具有π键的富勒烯Ｃ６０的温差谱峰为负值，负峰的强度样品温差增大而负荷增大，负峰的峰位无明显移。     

荧光素及其衍生物电子结构与光谱性质的理论研究

用ZINDO、从头算和密度泛函理论方法研究荧光素及其衍生物的电子结构和光谱性质.计算结果表明母体双阴离子荧光素分子(1)与单(2)、双(3)取代形成的单阴离子荧光素分子的基态电子结构不同,而且1与2和3的基态和激发态的电子转移方向相反.体系1~3的最大吸收波长依次发生红移,与实验结果相符合.     

C74(BN)2的UV和IR 光谱研究

Equilibrium geometries of 16 possible isomers for C74（BN）2 were studied by INDO series of methods, to indicate that the most stable three geometries are those where boron and nitrogen atoms substitute carbon atoms located at the same hexagon near the longest axis of C78 （C2v） to form B-N-B-N unit. Electronic spectra of C74（BN）2 were investigated with INDO/CIS method. The reason for the red shift of UV absorptions for C74（BN）2 compared with those of C78 （C2v） was discussed. IR spectra for 9,8,28,29-C74（BN）2 and 28,29,30,31-C74（BN）2 were calculated on the basis of AM1 geometries.     

The Effect of cis-trans Isomerism on the Electronic-vibrational Structure of the Ground and Excited States and Reactivity of 2-(2-Furyl)- and 2-(2-Thienyl)oxazole

The fluorescent properties, structure, and electronic structure of the ground and excited singlet and triplet electronic states of the cis and trans forms of 4,5-dihydro-2-(2-furyl)oxazole, 4,4-dihydro-2-(2-thienyl)oxazole, 2-(2-furyl)oxazole (FO), and 2-(2-thienyl)oxazole (TO) have been studied. The orbital nature of the lower excited singlet and triplet states has been studied by the semiempirical INDO/S (valence approximation) and PPP/S ( approximation) methods. It was shown that for FO and TO molecules the lower triplet state is of the * type, for which delocalization of the electronic excitation on atoms is characteristic. In the singlet excitation state inversion was observed of the energy levels of the delocalized * states and n* states localized over several bonds (for the free TO and FO molecules the lower excited singlet states S₁* were assigned to * and n* types respectively). Owing to the low position of the T * and T _n* levels relative to the singlet level of * type, the rate constant for intercombination conversion is greater than the rate constant for radiative decay. Consequently an efficient population of the triplet states of the molecules occurs under conditions of electronic-vibrational excitation. The direction of reactions during synthesis was compared with the localization indices in the ground state for electrophilic, nucleophilic, and radical substitution, and also with the excitation localization numbers L for a wide selection of electronically excited states. It was concluded that the change in the structure of the azole molecule on replacing an O atom by an S atom, or on changing from a partially hydrogenated to a heteroaromatic system, was the main reason for the change of all the spectral parameters characterizing the electronic-vibrational or the spin-orbital interaction of the most reactive groups of atoms in the molecular structure.     

Basicity of 2-phenyl-5-R-1,3,4-oxadiazoles

We have studied the basicity of 2-phenyl-5-R-1,3,4-oxadiazoles (R = H, Me, CH₂Ph, t-Bu, CH₂Cl, CCl₃, CF₃) in aqueous sulfuric acid solutions. These compounds are weak organic bases (pK_BH ⁺ is −1.8 to −5.2). The values of pK_BH ⁺ determined on the H₀ and X acidity function scales agree well with each other. The substituent at the 5 position has a substantial effect on the basicity of the 1,3,4-oxadiazole ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 748–756, May, 2006.     

含芯电子相关能修正的G2理论——G2(ful)

A general method in considering the core electronic correlation energies has been proposed and introduced into the standard Gaussian-2 (G2)[7] theory by small post-Hartree-Fock calculations. In this paper an additional MP2(FC)/6-31G(d) calculation over the G2 procedures is employed and examined in modification in modification to the flaw of Frozen-Core (FC) approximation of G2 vai eq.:
ΔE(full)= E[MP2(full)/6-31G(d)]-E[MP2(FC)/6-31G(d)]
where the MP2(full)/6-31G(d) energy has been obtained in the molecular geometry optimizations. This energy, ΔE(full), is directly added into the total G2 energy of a molecule in facilitating the effect of core electronic correlations for each molecule in chemical reactions. It has been shown that the over-all average absolute deviation for the 125 reaction energies of the G2 test set (test set 1) is slightly reduced from 5.09 to 5.01 kJ, mol(-1) while for the 55 D0 values, which have been used for the derivation of the A coefficient of the empirical High-Level...更多-Correction (HLC), it is also reduced from 4.99 [for both G2 and G2(COMPLETE)[8]]to 4.77 kJ• mol(-1). In addition, larger errors (greater than ±8.4 kJ•mol(-1) for the D0 energies are improved, especially for the largest error of the D0 of SO2 This error is reduced from 21.3 to 15.4 kJ. mol(-1), in which the experimental geometry would further reduce it by 7.1kJ.mol(-1)[8]. Another improvement is the absolute value of the A coefficient in HLC being reduced from 4.81 for G2 to 4.34 milli-hartrees which is believed to be useful in isolating the relationship between the HLC and the FC approximation. Modifications to the original G2 from this work is denoted as G2(fu 1) and thus the G2 (fu 1) total energy for a molecule is
E[G2(fu 1)]= E[G2]+Δ E(full)h
with a new ΔE[HLC] =-0.19α- 4.34nβ milli-hartree.     

有机-无机纳米复合材料光谱与电子性质研究进展

有机-无机纳米复合材料的研究在当前纳米科学技术的发展中占有重要地位，开创了材料与催化科学研究的新纪元。自从10年前首次合成纳米孔无机材料MCM-41至今，该领域研究不断深入，已展现出广阔的应用前景。当客体有机分子分散于纳米孔道内部时，其分子性质将产生明显变化。本文结合作者近期研究成果，力图从实验与理论两方面阐明在纳米复合体系中客体分子性质变化的原因。     

Me4Bzo2[14]六烯(2-)N4金属配合物的结构和反应性研究——Ⅱ. ML和MLXx型配合物的电子吸收光谱研究

本文研究了ML及MLX_x型配合物电子吸收光谱的电荷转移谱带,求得了所用N₄大环配体的光学电负性值,证实金属的形式D_q值与成键有关.对阐明有关化合物的结构提供了新的证据.     

Theoretical Study of the C_(60)O_3 Isomers

WiththepreparationandisolationofC,,O.'moreandmoreattentionwaspaidtotheirstructuresandpropertiest').WooddetectedC,,O.firstwhentheypreparedC,,byvaporizinggraphite").Fromthenon,thelaboratoriesallovertheworldhavepreparedC6,O.byvariousmethodssuchasPhotoxidationt2-4),Electrochemicaloxi-dation[si,Ozonizationt7.83andChemicaladditiont6'12-14iandsoon.Accordingtothefollow-uptheoreticalstudiesforC,,O.,itisindicatedthattherearetwoisomersofC,,O:eithertheoxygenatomislocatedoverthe6/6bondtogeneratethe6/…     

The role of quantum interference in determining transport properties of molecular bridges

An analytical approach to the electron transport phenomena in molecular devices is presented. The analyzed devices are composed of various molecular bridges attached to two semi-infinite electrodes. Molecular system is described within the tight-binding model, while the coupling to the electrodes is analyzed through the use of Newns-Anderson chemisorption theory. The current-voltage (I-V) characteristics are calculated through the integration of transmission function in the standard Landauer formulation. The essential question of quantum interference effect of electron waves is diseussed in three aspects: (i) the geometry of a molecular bridge, (ii) the presence of an external magnetic field and (iii) the location of chemical substituent.