VALENCE STATE OF C AtOMS AND σ_t-η_n SEPARABILITY OF MOLECULAR ORBITALS IN THE (BUCKMINSTER)FULLERENE C_(50)

The valence state of C atoms and the structure of molecular orbitals of the (Buckminster)Fullerene C_(60)have been demonstrated. It has been shown that when a motion-coordinate system is adopted, in which the coordinate origin is at every C atom, the z axis is in the direction of the normal and the (x,y) axes are in the direction of tangents of C_(60)'s spherical surface, 240 valence atomic orbitals of C_(60) can be divided into two groups. All (P_x, P_y)atomic orbitals named as Pt ones and all the other P_z atomic orbitals named as p. ones, That is to say that if we name the molecular orbital linearly combined of P_t atomic orbitals as σ_t and the molecular orbital linearly combined of P_n atomic orbitals as π_n, the 240 valence molecular orbitals are of the property of σ_t-π_n separability. It has also been shown that the frontier and nearby frontier molecular orbitals are π_n ones, and therefore the essential physical and chemical properties of C_(60) are determined by its π_n molecular orbitals.

Modified Atomic Orbital Calculations of Energy of the(2s^(2)^(1)S)Ground-State,the(2p^(2)^(1)D);(3d^(2)^(1)G)and(4f^(2)^(1)I)Doubly Excited States of Helium Isoelectronic Sequence from H-to Ca^(18+)

We report in this paper the ground-state energy 2s^(2)^(1)S and total energies of doubly excited states 2p^(2)^(1)D,3d^(2)^(1)D,4f^(2)^(1)I of the Helium isoelectronic sequence from H-to Ca^(18+).Calculations are performed using the Modified Atomic Orbital Theory(MAOT)in the framework of a variational procedure.The purpose of this study required a mathematical development of the Hamiltonian applied to Slater-type wave function[1]combining with Hylleraas-type wave function[2].The study leads to analytical expressions which are carried out under special MAXIMA computational program.This first proposed MAOT variational procedure,leads to accurate results in good agreement as well as with available other theoretical results than experimental data.In the present work,a new correlated wave function is presented to express analytically the total energies for the 2s21S ground state and each doubly 2p^(2)^(1)D,3d^(2)^(1)D,4f^(2)^(1)I excited states in the He-like systems.The present accurate data may be a useful guideline for future experimental and theoretical studies in the(nI^(2))systems.

Relativistic Reduction of the Electron-Nucleus Force in Bohr’s Hydrogen Atom and the Time of Electron Transition between the Neighbouring Quantum Energy Levels

The aim of the paper is to get an insight into the time interval of electron emission done between two neighbouring energy levels of the hydrogen atom. To this purpose, in the first step, the formulae of the special relativity are applied to demonstrate the conditions which can annihilate the electrostatic force acting between the nucleus and electron in the atom. This result is obtained when a suitable electron speed entering the Lorentz transformation is combined with the strength of the magnetic field acting normally to the electron orbit in the atom. In the next step, the Maxwell equation characterizing the electromotive force is applied to calculate the time interval connected with the change of the magnetic field necessary to produce the force. It is shown that the time interval obtained from the Maxwell equation, multiplied by the energy change of two neighbouring energy levels considered in the atom, does satisfy the Joule-Lenz formula associated with the quantum electron energy emission rate between the levels.

Principle for the Working of the Lithium-Ion Battery

The technological advances in Lithium-ion batteries have created many new applications, including electric vehicles. In this short note, we shall explain in simple terms the basic physics why and how it is possible to have high energy capacity in Lithium-ion batteries. However, heating has been a common problem and without appropriate design, they might give fire and explosion as reported.

Variational Calculation of the Doubly-Excited States Nsnp of He-Like Ions via the Modified Atomic Orbitals Theory

In this paper, we have declined the formalism of the method of the Modified Atomic Orbital Theory (MAOT) applied to the calculations of energies of doubly excited states 2snp, 3snp, and 4snp Helium-like systems. Then we also applied the variational procedure of the Modified Atomic Orbital Theory to the computations of total energies, excitation energies of doubly-excited states 2snp, 3snp, 4snp types of Helium-like systems. The results obtained in this work are in good agreement with the experimental and theoretical values available.

Electron Momentum Spectroscopy of Ethanethiol Complete Valence Shell

The binding energy spectra and electron momentum distributions for the complete valence orbitals of ethanethiol were measured for the first time by binary （e, 2e） electron momentum spectroscopy employing non-coplanar symmetric kinematics at an impact energy of 1200 eV plus binding energy. The experimental results are generally consistent with the theoretical calculations using density functional theory and Hartree-Fock methods with various basis sets. A possible satellite line at 17.8 eV in binding energy spectrum was observed and studied by electron momentum spectroscopy.

Exploring the effect of aggregation-induced emission on the excited state intramolecular proton transfer for a bis-imine derivative by quantum mechanics and our own n-layered integrated molecular orbital and molecular mechanics calculations

We theoretically investigate the excited state intramolecular proton transfer(ESIPT) behavior of the novel fluorophore bis-imine derivative molecule HNP which was designed based on the intersection of 1-(hydrazonomethyl)-naphthalene-2-ol and 1-pyrenecarboxaldehyde. Especially, the density functional theory(DFT) and time-dependent density functional theory(TDDFT) methods for HNP monomer are introduced. Moreover, the "our own n-layered integrated molecular orbital and molecular mechanics"(ONIOM) method(TDDFT:universal force field(UFF)) is used to reveal the aggregation-induced emission(AIE) effect on the ESIPT process for HNP in crystal. Our results confirm that the ESIPT process happens upon the photoexcitation for the HNP monomer and HNP in crystal, which is distinctly monitored by the optimized geometric structures and the potential energy curves. In addition, the results of potential energy curves reveal that the ESIPT process in HNP will be promoted by the AIE effect. Furthermore, the highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) for the HNP monomer and HNP in crystal have been calculated. The calculation demonstrates that the electron density decrease of proton donor caused by excitation promotes the ESIPT process. In addition, we find that the variation of atomic dipole moment corrected Hirshfeld population(ADCH) charge for proton acceptor induced by the AIE effect facilitates the ESIPT process. The results will be expected to deepen the understanding of ESIPT dynamics for luminophore under the AIE effect and provide insight into future design of high-efficient AIE compounds.

Photoionization Study of Cl II, Ar II and Kr II Ions Using the Modified Atomic Orbital Theory

Resonance energies of the Cl II-[3s23p3(2D5/2)]nd and [3s23p3(2P3/2)]nd, Ar II-3s23p4(1D2)ns, nd and of the Kr II [4s24p4(1D2)]ns, nd and 4s24p4(3P2,3P1)]ns, 4s24p4(3D2)]ns, nd and 4s24p4(3D2, 1S0)]ns, nd Rydberg series are reported. Natural widths of the Ar II-[3s23p4(1D2)]ns, nd series are also reported. Calculations are done in the framework of the Modified Atomic Orbital Theory (MAOT). Excellent agreements are obtained with available theoretical and experimental data. High lying accurate resonance energies up to n = 40 are tabulated. The possibility to use the MAOT formalism report rapidly with an excellent accuracy the position of the excitation resonances as well as their width within simple analytical formulae is demonstrated.

Low-lying electronic states of aluminum monoiodide

High-level ab initio calculations of aluminum monoiodide(AlI) molecule are performed by utilizing the multireference configuration interaction plus Davidson correction(MRCI+Q) method. The core-valence correlation(CV) and spin–orbit coupling(SOC) effect are considered. The adiabatic potential energy curves(PECs) of a total of 13 Λ–S states and 24 ? states are computed. The spectroscopic constants of bound states are determined, which are in accordance with the results of the available experimental and theoretical studies. The interactions between the Λ–S states are analyzed with the aid of the spin–orbit matrix elements. Finally, the transition properties including transition dipole moment(TDM),Frank–Condon factors(FCF) and radiative lifetime are obtained based on the computed PEC. Our study sheds light on the electronic structure and spectroscopy of low-lying electronic states of the AlI molecule.

Extending the Standard Model in Hyper-Dimensional Mechanics

According to studies on the precursive time quantum variable, this publication presents an in-depth analysis of the chapter on the correlation between the nuclear mass and electroweak force. This research shows that there is a close correlation between the nuclear mass and the energy of the orbitals which underlies the electroweak interaction.

Theoretical Study on the Hydrogen Bonding Interactions in Complexes of 5-Hydroxytryptamine with Water

The energies, geometries and harmonic vibrational frequencies of 1 ： 1 5-hydroxytryptamine-water （5-HT-H20） complexes are studied at the MP2/6-311 ＋ ＋ G（d,p） level. Natural bond orbital （NBO）, quantum theory of atoms in molecules （QTAIM） analyses and the localized molecular orbital energy decomposition analysis （LMO-EDA） were performed to explore the nature of the hydrogen-bonding interactions in these complexes. Various types of hydro- gen bonds （H-bonds） are formed in these 5-HT-H20 complexes. The intermolecular C4H55HT＇＂Ow H-bond in HTW3 is strengthened due to the cooperativity, whereas no such cooperativity is found in the other 5-HT-H20 complexes. H-bond in which nitrogen atom of amino in 5-HT acted as proton donors was stronger than other H-bonds. Our researches show that the hydrogen bonding interaction plays a vital role on the relative stabilities of 5-HT-H20 complexes.

Evaluation of Orbital- and Ground State Energies of Some Open- and Closed-Shell Atoms over Integer and Noninteger Slater Type Orbitals

Ab initio calculations of the orbital and the ground state energies of some open- and closed-shell atoms over Slater type orbitals with quantum numbers integer and Slater type orbitals with quantum numbers noninteger have been performed. In order to increase the efficiency of these calculations the atomic two-electron integrals were expressed in terms of incomplete beta function. Results were observed to be in good agreement with the literature.

基态原子价壳层电子能级连接性指数与元素的电负性

构建了基态原子价壳层电子能级连接性指数 (mVEI) ,m =0 ,1,2 ,… ,它对基态原子实现唯一性表征 ,其中0 VEI,1VEI对原子具有良好的结构选择性 .以0 VEI,1VEI,价壳层电子总离子化能 ( niEi)和总价电子数 ( ni)为基本参数 ,定义了元素的电负性 :XN=0 .44 40 6 7+1.190 6 5 3(1- 1.32 775 / ni) (0 VEI) - 3.15 46 75 (1VEI) +0 .134 5 91·( niEi/ ni) .用上式给出了周期表中主族元素、副族元素及惰性元素的电负性 .结果表明 ,新电负性标度XN 与目前流行的Pauling标度颇为一致 .进一步从价轨道能级连接性指数确定了碳原子的sp ,sp2 ,sp3 杂化轨道的电负性 .

一种电负性新标度:基态自由原子价壳层电子平均吸引能

原子吸引价电子的总能力可由基态自由原子的价电子离子化能（ＴＩＥ＝ΣｎｉＥｉ）及其电子亲合能（ＥＡ）之和来度量。该和值亦称为总吸引能，记为ＴＡＥ＝ΣｎｉＥｉ＋ＥＡ，此处Ｅｉ为基态自由原子价壳层电子的离子化能，Σｎｉ为与之相关的价壳层电子数，ＥＡ则是电子亲合能。所指出的新电负性标度χＣＬ与总吸引能ＴＡＥ除以原子价壳层电子数目Σｎｉ之值即平均吸引能成正比：χＣＬ＝０．１８１３ＡＡＥ＝０．１８１３ＴＡＥ／Σｎｉ＝０．１８１３（ΣｎｉＥｉ＋ＥＡ）／Σｎｉ，进一步从原子总吸引能ＴＡＥ可确定其价轨道电负性。

Fe、Co、Ni双齿巯基配合物从头算研究

运用Gaussian94量子化学程序包，采用LanL2DZ基组，对Fe（Ⅲ）、Co（Ⅲ）、Ni（Ⅱ）与Hmpo（2-巯基氧化吡啶）的双齿配合物Fe（mpo）3、Co（mpo）3、Ni（mpo）2进行从头算研究。讨论这些配合物的稳定性、分子轨道能量、原子电荷分布以及最高占据轨道的特征等，为过渡金属双齿配合物的合成、结构分析及其在酶与蛋白质中的活性部位研究提供一些理论参考．

N-(邻氯苯基)苯甲酰胺在CuX(X=I,Br)催化下的分子内O-芳基化反应机理

采用密度泛函理论(DFT)中的B3LYP方法,在6-31+G*基组水平上研究了N-(邻氯苯基)苯甲酰胺在CuX(X=I,Br)催化下发生分子内O-芳基化的反应机理.优化了反应过程中的反应物、中间体、过渡态和产物,通过能量和振动分析证实了中间体和过渡态的真实性.并且在相同基组水平上应用自然键轨道(NBO)理论和分子中的原子(AIM)理论分析了这些化合物的成键特征和轨道间的相互作用.比较了两种不同铜盐催化剂的催化活性,计算结果表明两种催化剂的反应路径和反应的控制步骤完全相同,在CuBr催化下标题化合物控制步骤的活化能比在CuI催化下的低,证明了CuBr的催化活性要比CuI的高一些,与实验结果一致.

拓扑指数^mE及其对无机物理化性质的预测

为了预测无机物的一些理化性质,修改了Randic拓扑指数的点价值δi,构建了价电子轨道能量拓扑指 数mE.用其0、1阶指数0E、1E与无机氢化物的pKa1值、20种碱金属卤化物的晶格能U、生成焓△rHm、水化能 △rGmθ、核间距R0相关联,拟合的回归方程的相关系(指)数分别为0.9944(0.9958)、0.9967(0.9971)、0.9816 (0.9816)、0.9791(0.9795)、0.995 3(0.995 3),满足优级或良级标准.预测取得了较好的结果.

价层轨道平均能与掺杂二硼化镁体系超导电性的关系

研究了不同掺杂组分二硼化镁超导体的超导电性和原子价层轨道平均能的关系,发现全部阳离子和阴离子的价层轨道平均能的平均值主要集中在9.9ev至10.35ev之间,阳离子之间与阴离子价层轨道平均能的平均值之差都集中在在3.1ev至4.4ev之间.这种关系将有助于了解晶格上电子的静电作用与超导机理之间的关系。

价电子轨道能量指数^mE与无机氢化物酸性的相关性

为了研究无机氢化物的HaA酸性变化规律,构建了价电子轨道能量拓扑指数mE.利用其0、1阶指数0E、1E以及A原子的电负性xA与13种p区无机氢化物的pKa1关联,拟合成4个回归方程.相关系数和复相关系数分别为0.9961、0.9961、0.9964和0.9963.预测取得了良好的结果.

一种价态元素电负性的新标度

本文利用原子的价层轨道能、共价半径和有效主量子数为主要参数,以静电力为基础计算了价态元素电负性,本文计算了78种元素常见价态的电负性,由此,产生了一套价态元素电负性的新标度,其计算公式为:■式中Ei为原子的价层轨道能,rc为原子的共价半径,n*为有效主量子数。该标度不但容易理解和计算,而且标度值比已有的文献值更接近传统的鲍林电负性值。此外,该标度值的相对大小还能反映配合物的稳定性,过渡金属收缩和镧系元素收缩等性质。