铁离子在水中的颜色与其电子结构等因素的关系

从电子结构及离子极化等方面深入研究并解释了Fe(Ⅲ)在水溶液中所呈现的不同颜色.明确指出由于自由Fe(Ⅲ)离子的基组态电子结构为3d5,其电子跃迁(d-d跃迁)都是自旋禁阻的,导致对可见光吸收很弱,所以水合铁离子呈浅紫色(近无色),即水合铁离子的颜色与其电子结构相关;而Fe(Ⅲ)的氯配合物及羟基水合配离子呈黄色为离子极化导致电荷跃迁吸收部分可见光所致.     

晶体中离子的电子极化率的新计算法

极化效应对晶体的宏观性质影响很大,人们对它进行了大量的研究工作。利用Lorentz公式确定分子极化率的方法已较为成熟,但是该方法只能给出分子、元胞和键体积等单位体积的极化率,在这些单位体积中至少包括两种离子,所以它不能确定每个离子的极化行为。为了求得离子的电子极化率曾提出过许多近似方法,如假定阳离子极化小,它和自由状态差别不大,主要是阴离子极化,故用自由状态阳离子的极化率代替其在晶体中的极化率进而求     

稀土化合物晶体的化学键和光谱效应

计算了稀土化合物晶体的化学键参数和离子极化率,讨论了基质对稀土离子的电子云扩大效应和超灵敏跃迁的影响机理。     

利用基于Gouy-Chapman模型的离子有效电荷定量表征离子特异性效应

离子特异性效应在固-液界面反应中是普遍存在的.近期研究指出,在较低电解质浓度的某些体系中,离子特异性效应可能并非来源于色散力、经典诱导力、离子半径或水合半径的大小等,而是界面附近强电场中的离子极化作用.这种作用可使界面附近的吸附态反号离子被强烈极化(高达经典极化的104倍).强烈极化的结果将导致离子在界面附近受到的库仑力远远超过离子电荷所能产生的库仑力,这体现在离子的有效电荷将远大于离子的实际电荷.因此胶体体系中基于这种强极化的离子有效电荷可以用来定量表征离子特异性效应的强度.本研究在蒙脱石-胡敏酸混合悬液凝聚过程中发现了Na+、K+、Ca2+、Cu2+四种离子的离子特异性效应,提出了基于激光散射技术测定离子有效电荷的方法,并成功获得了被强烈极化后的离子有效电荷数值.实验测得的Na+、K+、Ca2+、Cu2+四种离子的有效电荷值分别为:ZNa(effective)=1.46,ZK(effective)=1.86,ZCa(effective)=3.92,ZCu(effective)=6.48.该结果表明:(1)离子在强电场中的极化将大大提高离子的有效电荷,从而极大地增强离子所受的库仑作用力;(2)离子的电子层数越多,离子极化越强烈,离子的有效电荷增加越多.     

Ca2B2O5的电子结构和能带结构

合成了标题化合物,在已测晶体结构的基础上,利用含组态作用的INDO/S方法计算了其他电子能带结构;利用态求和方法计算了微结构分子的线性极化率及其晶体的平均折射率。分析结果表明,价带主要由B^3^+和O^2^-离子的价轨道的贡献,导带底部主要由Ca^2^+离子轨道的贡献,从O^2^-离子到Ca^2^+离子的电荷转移对线性极化率起主要贡献。     

利用基于Gouy-Chapman模型的离子有效电荷定量表征离子特异性效应

离子特异性效应在固-液界面反应中是普遍存在的. 近期研究指出, 在较低电解质浓度的某些体系中, 离子特异性效应可能并非来源于色散力、经典诱导力、离子半径或水合半径的大小等, 而是界面附近强电场中的离子极化作用. 这种作用可使界面附近的吸附态反号离子被强烈极化(高达经典极化的10⁴倍). 强烈极化的结果将导致离子在界面附近受到的库仑力远远超过离子电荷所能产生的库仑力, 这体现在离子的有效电荷将远大于离子的实际电荷. 因此胶体体系中基于这种强极化的离子有效电荷可以用来定量表征离子特异性效应的强度. 本研究在蒙脱石-胡敏酸混合悬液凝聚过程中发现了Na⁺、K⁺、Ca²⁺、Cu²⁺四种离子的离子特异性效应, 提出了基于激光散射技术测定离子有效电荷的方法, 并成功获得了被强烈极化后的离子有效电荷数值. 实验测得的Na⁺、K⁺、Ca²⁺、Cu²⁺四种离子的有效电荷值分别为: Z_{Na(effective)}=1.46, Z_K(effective)=1.86, Z_{Ca(effective)}=3.92, Z_{Cu(effective)}=6.48.该结果表明: (1) 离子在强电场中的极化将大大提高离子的有效电荷, 从而极大地增强离子所受的库仑作用力;(2) 离子的电子层数越多, 离子极化越强烈, 离子的有效电荷增加越多.     

6,6’-二氧-3,3’-二四联氮自由基及其衍生物不同构象 NLO性质的DFT研究

运用密度泛函理论(DFT) UB3LYP和有限场(FF)方法, 探讨了6,6’-二氧-3,3’-二四联氮自由基及其衍生物构象变化对非线性光学性质的影响, 分析了自由基分子极化率、二阶超极化率对构象、自旋多重度的依赖关系. 结果表明, 不同构象下各体系有效交换积分值都小于零, 自由基间表现为反铁磁性耦合. 各体系单三态不同构象时极化率α值的变化很小, 且不同构象时单重态的α值都大于三重态. 在构象变化过程中, 体系(a)和(b)单重态的二阶超极化率均为负值(体系(a)的45°和135°除外), 且绝对值都小于三重态的二阶超极化率值, 体系(c)的单三重态二阶超极化率值均为正值, 且在分子接近平面构型时, 三重态的γ值大于单重态. 不同的取代基R, 对体系的构型、极化率和二阶超极化率的影响也不同.     

Tb3+离子4f75d组态能级的电子云扩大效应

研究了电子云扩大效应对Tb3+离子5d能级的影响. 利用光谱理论, 将电子云扩大效应比率β同Tb3+离子4f75d组态的自旋允许和禁阻跃迁能级的能级差联系起来, 通过复杂晶体化学键理论确定了化学键的共价性、 相应键体积极化率以及配体离子的有效电荷与β的线性关系, 同时得到了对β有影响并与Tb3+离子自身相关的因子.     

钪和钇二价离子跃迁几率和振子强度的理论计算

利用最弱受约束电子势模型理论计算了二价钪离了和二价钇离子的能级间跃迁几率和振子强度的数值．二价钪离子的计算结果与美国国家标准技术研究院（NIST）所给出的可接受值吻合良好二价钇离子的计算结果也与现有的其他理论方法的计算结果十分接近．     

神经网络和Eu^2＋离子在复合氟化物基体中跃迁发射的研究

运用人工神经网法对复合氟化物中Ｅｕ＾＋离子光谱结构进行了分类研究，对神经网络的基本特征进行了观察。实验表明，神经网的结构、初始权重以及作为训练集和预测集的随枘发组对最终结果都会产生重要影响。本研究采用测试集来监控训练过程，以避免“过训练”，并提高神经网的预测性能。     

Electrophoretic evidence for a new type of counterion condensation

A systematic capillary electrophoresis study uncovered how polyelectrolyte effective charge density varies with backbone charge spacing and solvent dielectric constant. The study primarily focused on aliphatic ionenes, a special class of polyelectrolytes, which possess regularly spaced quaternary ammonium groups in the backbone. Complete ionization of functional units and good solvency in water or mixtures of water with lower dielectric constant solvents (methanol, acetonitrile) enabled continuous measurements of ionene effective charge density through the onset of counterion condensation. Ionenes with both uniform and alternating charge spacing were examined. As expected, effective charge density rose linearly with fixed charge density to a critical value, above which effective charge density remained constant. Deviating from expectation, the onset of condensation did not occur at a critical fixed charge density. Instead, condensation initiated at a constant critical Bjerrum length. The same onset condition was found for quaternized poly(vinyl pyridine)s. These experimental results suggest a new form of condensation, one driven by ion-pairing of polyelectrolyte with counterions. In support of this hypothesis, the onset of condensation appeared to correlate with counterion size. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3616–3627, 2004     

Bond stretching force constants and compressibilities of nitride,oxide, and sulfide coordination polyhedra in molecules and crystals

Molecular quadratic stretching force constants are calculated for a variety of MX bonds (X = N, O, S) in coordinated polyhedra containing row 1 and 2 metal atoms, M, using SCF molecular orbital methods and 6-31G^* basis sets. The resulting data scatter along three distinct trends, depending on whether the bonds involve row 1 atoms, row 1 and row 2 atoms, or row 2 atoms. When compared with spectroscopically determined force constants, the calculated force constants are found to be 20% larger. A single trend seems to obtain when the calculated force constants are plotted as a function of the effective nuclear charges of the bonded atoms and their interatomic separations. Scaled force constants calculated for the SiO bond are in rough agreement with values provided by spectroscopic measurements for silicic acid molecules and silicate crystals. Polyhedral compressibilities for nitride-, oxide-, and sulfide-coordinated polyhedra are inversely related with force constants calculated for their MX bonds. The close similarity of these compressibilities and those recorded for chemically similar crystals suggests that force constant-compressibility relationships in chemically similar molecular and crystalline systems are not significantly different.     

Charge control of the complex formation of phenol with unsaturated compounds containing organoelement substituents from group IV

The frequency shifts (v (OH)) of phenol and the resonance components (v_r) of these shifts in the IR spectra of forty H-complexes of phenol with furan derivatives containing organic, organosilicon, organogermanium, and organotin substituents are studied. The values of v and v_R are linearly related to quantum chemical parameters of the variation of the effective charges of the furan ring atoms affected by - and -interactions with organic substituents. The effect of the conjugation between an organoelement substituent and the furan ring on the effective charges is estimated. The resonance parameters (_R) of organoelement substituents in derivatives of benzene, thiophene, and furan and the reasons for the non-versatility of _R are considered.For report 7, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 289–295, February, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-18372).     

Catalytic activity correlation of Ni(II), Co(II) and Pd(II) complexes to metal atom net charge

The metal atom net charge correlation (MANCC) method was developed in prediction of catalyst activity of asymmetric late-transition metal complexes, 2-quinoxalinyl-6-iminopyridine Ni (II), 2-imino-1, 10-phenanthroline Co(II) and 2-methoxycarbonyl-6-iminopyridine Pd(II) complexes, from the net charge of the metal atom for ethylene polymerization. Dreiding force field was modified according to the X-ray diffraction data. We found that the asymmetric structure of the complexes resulted in a charge difference between two halogen atoms coordinated to the metal atom. In order to remove such contribution we introduced the effective charge Q _eff, which was obtained by the charge equilibration (QEq) approach. The results verified the successful introduction of Q _eff and showed that the catalytic activities of different complexes are related to central metal atom effective charge. Supported by the National Natural Science Foundation of China (Grant Nos. 90612015, 20674090, and 20474073), and 973 Project (Grant No. 2004CB720606)     

Correlations between the quantum-chemical parameters of amino acids and regioselectivity of isotope exchange with the spillover hydrogen

The effective charges and the proton affinity of carbon atoms of α-amino acids were calculated by quantum-chemical methods. The relative reactivity of the C−H bonds of amino acids under conditions of high-temperature solid-state catalytic isotope exchange (HSCIE) was studied. Correlations between the electron structure of amino acids and the regioselectivity of the solid-state isotope exchange were established. The reactivity of the carbon atoms with high proton affinity increases under HSCIE conditions. An assumption was made that the interaction of a solid organic compound with the spillover hydrogen can be described as the electrophilic substitution at the saturated and aromatic carbon atoms. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1611–1617, September, 1997.     

Determination of the C4-H bond dissociation energies of NADH models and their radical cations in acetonitrile

Heterolytic and homolytic bond dissociation energies of the C4-H bonds in ten NADH models (seven 1,4-dihydronicotinamide derivatives, two Hantzsch 1,4-dihydropyridine derivatives, and 9,10-dihydroacridine) and their radical cations in acetonitrile were evaluated by titration calorimetry and electrochemistry, according to the four thermodynamic cycles constructed from the reactions of the NADH models with N,N,N',N'-tetramethyl-p-phenylenediamine radical cation perchlorate in acetonitrile (note: C9-H bond rather than C4-H bond for 9,10-dihydroacridine; however, unless specified, the C9-H bond will be described as a C4-H bond for convenience). The results show that the energetic scales of the heterolytic and homolytic bond dissociation energies of the C4-H bonds cover ranges of 64.2-81.1 and 67.9-73.7 kcal mol(-1) for the neutral NADH models, respectively, and the energetic scales of the heterolytic and homolytic bond dissociation energies of the (C4-H)(.+) bonds cover ranges of 4.1-9.7 and 31.4-43.5 kcal mol(-1) for the radical cations of the NADH models, respectively. Detailed comparison of the two sets of C4-H bond dissociation energies in 1-benzyl-1,4-dihydronicotinamide (BNAH), Hantzsch 1,4-dihydropyridine (HEH), and 9,10-dihydroacridine (AcrH(2)) (as the three most typical NADH models) shows that for BNAH and AcrH(2), the heterolytic C4-H bond dissociation energies are smaller (by 3.62 kcal mol(-1)) and larger (by 7.4 kcal mol(-1)), respectively, than the corresponding homolytic C4-H bond dissociation energy. However, for HEH, the heterolytic C4-H bond dissociation energy (69.3 kcal mol(-1)) is very close to the corresponding homolytic C4-H bond dissociation energy (69.4 kcal mol(-1)). These results suggests that the hydride is released more easily than the corresponding hydrogen atom from BNAH and vice versa for AcrH(2), and that there are two almost equal possibilities for the hydride and the hydrogen atom transfers from HEH. Examination of the two sets of the (C4-H)(.+) bond dissociation energies shows that the homolytic (C4-H)(.+) bond dissociation energies are much larger than the corresponding heterolytic (C4-H)(.+) bond dissociation energies for the ten NADH models by 23.3-34.4 kcal mol(-1); this suggests that if the hydride transfer from the NADH models is initiated by a one-electron transfer, the proton transfer should be more likely to take place than the corresponding hydrogen atom transfer in the second step. In addition, some elusive structural information about the reaction intermediates of the NADH models was obtained by using Hammett-type linear free-energy analysis.     

Catalytic activity correlation of Ni(Ⅱ),Co(Ⅱ) and Pd(Ⅱ) complexes to metal atom net charge

The metal atom net charge correlation(MANCC) method was developed in prediction of catalyst activity of asymmetric late-transition metal complexes,2-quinoxalinyl-6-iminopyridine Ni(Ⅱ),2-imino-1,10-phenanthroline Co(Ⅱ) and 2-methoxycarbonyl-6-iminopyridine Pd(Ⅱ) complexes,from the net charge of the metal atom for ethylene polymerization.Dreiding force field was modified according to the X-ray diffraction data.We found that the asymmetric structure of the complexes resulted in a charge differ-ence between two...     

Diabatic investigation for the NaRb molecule

An extensive diabatic investigation of the NaRb species has been carried out for all excited states up to the ionic limit Na^‐Rb⁺. An ab initio calculation founded on the pseudopotential, core polarization potential operators and full configuration interaction has been used with an efficient diabatization method involving a combination of variational effective hamiltonian theory and an effective overlap matrix. Diabatic potential energy curves and electric dipole moments (permanent and transition) for all the symmetries Σ⁺, Π, and Δ have been studied for the first time. Thanks to a unitary rotation matrix, the examination of the diabatic permanent dipole moment (PDM) has shown the ionic feature clearly seen in the diabatic ¹Σ⁺ potential curves and confirming the high imprint of the Na^‐Rb⁺ ionic state in the adiabatic representation. Diabatic transition dipole moments have also been computed. Real crossings have been shown for the diabatic PDM, locating the avoided crossings between the corresponding adiabatic energy curves.     

A new scale of atomic electronegativities

A new formula for the calculation of atomic electronegativities from the atomic size and nuclear effective charge is proposed. The formula has the same dimensionality as the one used for the thermochemical scale. The calculated ionic and van der Waals atomic electronegativities are used for the interpretation of the bond nature in binary and coordination compounds (in particular, the bond ionicity is calculated in molecules and crystals of the AB type).Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 32–37, January, 1993.     

Counterion mobility and effective charge of polyelectrolytes in solution

Polyelectrolytes are macromolecules containing dissociable or charged groups. The charge, that is effectively accessible, is determined by counterion condensation, which is strongly influenced by the ionic strength of the solution under study. In general a rapid exchange between free and condensed counterions is expected. In the present study diffusion and electrophoretic mobility of poly(diallyldimethylammoniumchloride) and perfluorinated succinic acid have been monitored simultaneously. Condensation of the perfluorinated succinic acid to the macroion shows in the electrophoretic mobility of succinic acid monitored by pulsed field gradient NMR. In the concentration dependence of the averaged diffusion coefficient and electrophoretic mobility an exchange fast on the time scale of the NMR experiment is manifested.