Coherence of the Even-Odd Rule with an Effective-Valence Isoelectronicity Rule for Chemical Structural Formulas: Application to Known and Unknown Single-Covalent-Bonded Compounds

Ions or molecules are said to be isoelectronic if they are composed of different elements but have the same number of electrons, the same number of covalent bonds and the same structure. This criterion is unfortunately not sufficient to ensure that a chemical structure is a valid chemical compound. In a previous article, a procedure has been described to draw 2D valid structural formulas: the even-odd rule. This rule has been applied first to single-bonded molecules then to single-charged single-bonded ions. It covers hypovalent, hypervalent or classic Lewis’ octet compounds. The funding principle of the even-odd rule is that each atom of the compound possesses an outer-shell filled only with pairs of electrons. The application of this rule guarantees validity of any single-covalent-bond chemical structure. In the present paper, this even-odd rule and its electron-pair criterion are checked for coherence with an effective-valence isoelectronic rule using numerous known compounds having single-covalent-bond connections. The test addresses Lewis’ octet ions or molecules as well as hypovalent and hypervalent compounds. The article concludes that the even-odd rule and the effective-valence isoelectronicity rule are coherent for known single-covalent-bond chemical compounds.

Oscillator strengths for 2 ~2S-n^2P transitions of the lithium isoelectronic sequence from Z=11 to 20

The dipole-length, dipole-velocity and dipole-acceleration absorption oscillator strengths for the 1s^22s-1s^2np （3 ≤ n ≤9） transitions of lithium-like systems from Z = 11 to 20 are calculated by using the energies and the multiconfiguration interaction wave functions obtained from a full core plus correlation method, in which relativistic and mass-polarization effects on the energy, as the first-order perturbation corrections, are included. The results of three forms are in good agreement with each other, and closely agree with the experimental data available in the literature. Based on the quantum defects obtained with quantum defect theory （QDT）, the discrete oscillator strengths for the transitions from the ground state to highly excited states 1s^2np （n ≥ 10） and oscillator strength densities corresponding to the bound-free transitions are obtained for these ions.

Intercombination transitions of the carbon-like isoelectronic sequence

Energy levels, wavelengths, transition rates, oscillator strengths, and lifetimes between the 2s22p23P1,2s22p23P2,and 2s2p35S2 levels of ions in the carbon-like （C-like） isoelectronic sequence （nuclear charges Z=7-92） are calculated in the valence and core-valence limits using the multiconfiguration Dirac–Fock method. The Breit interaction, quantum electrodynamics （QED）, and finite nuclear mass effects are taken into account in subsequent relativistic configuration-interaction calculations. The calculated energies and transition rates are compared with the critically evaluated experimental values and other recent calculated results. Our calculated data are in good agreement with these data.

Introducing an Extended Covalent Bond between Oxygen Atoms with an OXO-Shape in Ions and Molecules: Compatibility with the Even-Odd and the Isoelectronicity Rules

Building on the recent success of the even-odd rule, the present paper explores its implications by studying the very specific case of OXO compounds. These compounds are usually represented with double bonds linking two oxygen atoms to a central atom—as in carbon dioxyde—yet can sometimes be drawn in a triangular structure, such as in calcium dioxyde. Measurement data moreover indicate that most OXO compounds have an angle around 120° between oxygen atoms, although that seems incompatible with triangular representations. The aim here is to unify these commonly admitted representations by linking oxygen atoms through a single bond that is longer than usual covalent bonds: an “elongated bond”. This elongated bond has the interesting effect of suppressing the need for double bonds between oxygen and the central atom. The elongated bond concept is applied to about a hundred of molecules and ions and methodically compared to classical representations. It is shown that this new representation, associated to the even-odd rule, is compatible with all studied compounds and can be used in place of their classical drawings. Its usage greatly simplifies complex concepts like resonance and separated charges in gases. Elongated bonds are also shown to be practicable with the isoelectronic rule as well as isomers, and throughout chemical reactions. This study of an especially long and wide angle bond confirms the versatility of the even-odd rule: it is not limited to compounds with short covalent bonds and can include OO covalent bond lengths of more than 200 pm and with OXO angles above 90°.

Tailoring electronic properties of two-dimensional antimonene with isoelectronic counterparts

Using ab initio density functional theory calculations, we explore the three most stable structural phases, namely, α,β, and cubic(c) phases, of two-dimensional(2D) antimonene, as well as its isoelectronic counterparts SnTe and InI. We find that the band gap increases monotonically from Sb to SnTe to InI along with an increase in ionicity, independent of the structural phases. The band gaps of this material family cover the entire visible-light energy spectrum, ranging from 0.26 eV to 3.37 eV, rendering them promising candidates for optoelectronic applications. Meanwhile, band-edge positions of these materials are explored and all three types of band alignments can be achieved through properly combining antimonene with its isoelectronic counterparts to form heterostructures. The richness in electronic properties for this isoelectronic material family sheds light on possibilities to tailor the fundamental band gap of antimonene via lateral alloying or forming vertical heterostructures.

Ground state energy of He isoelectronic sequence treated variationally via Hylleraas-like wavefunction

In this study, the energy for the ground state of helium and a few helium-like ions （Z=1-6） is computed variationally by using a Hylleraas-like wavefunction. A four-parameters wavefunction, satisfying boundary conditions for coalescence points, is combined with a Hylleraas-like basis set which explicitly incorporates r12 interelectronic distance. The main contribution of this work is the introduction of modified correlation terms leading to the definition of integral transforms which provide the calculation of expectation value of energy to be done analytically over single-particle coordinates instead of Hylleraas coordinates.

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.

Oscillator Strengths for 2s~2-2p~2P Transitions of the Lithium IsoelectronicSequence from NaIX to CaXVIII

The nonrelativistic dipole-length, -velocity and -acceleration absorptionoscillator strengths for the 1s~22s-1s~22p transitions of the lithium isoelectronic sequence from Z= 11 to 20 are calculated by using the energies and the multiconfiguration interaction wavefunctions obtained from a full core plus correlation (FCPC) method. In most cases, the agreementbetween the oscillator strengths values from the length and velocity formula is up to four or fivedigit. Our results are aiso in good agreement with previous theoretical data available in theliterature.

THE ELECTRIC PROPERTY OF SINGLET CARBENE AND ITS ISOELECTRONIC SYSTEM^1——Electrophilic and Nucleophilic Directions of an Atom in the Molecule

The electrostatic potential of carbene and nitrene,have been calculated by AB INITIO method with 6-31G** basis set,there are positive potential regions in the directions of vacant P orbitals,and negative regions in the directions of lone-pair electrons. Therefore,atoms in these molecules have different electric properties in different directions.The idea of electrophilic and nucleophilic directions of an atom in molecules should be introduced.

Theoretical study on stability and nonlinear optical properties of tetrahydropyrrole diradical and its isoelectronic systems in different electronic states

The polarizabilities and hyperpolarizabilities of the tetrahydropyrrole diradical in different electronic states have been investigated using ab initio and density functional theory （DFT） methods combined with the finite field （FF） approach. The polarizability average value as is a maximum for the singlet state, while that for the closed-shell is a minimum. The trend in second hyperpolarizability average value yis in good agreement with that for as The yvalues of the singlet and triplet states are, respectively, about 3 and 2 times larger than that of the closed-shell. The order of the first hyperpolarizability total effective value βtot is βot （closed shell） βtot （singlet） 〉 βtot （triplet）. The as, βtot, and 7 values of different electronic states obtained using the B3LYP and MP4SDQ methods are close to those obtained using the reliable CCSD method. The nonlinear optical （NLO） properties of two systems isoelectronic with the tetrahydropyrrole diradical-cyclopentane and tetrahydrofuran diradicalsshow that the polarizabilities and hyperpolarizabilities of these systems are all smaller than those of the tetrahydropyrrole diradical in the three electronic states.

Exciton-Phonon Coupling of NN_3 Center in Heavily Nitrogen Doped GaP

Under heavy nitrogen doping,due to the “concentration quenching” effect,the full spectrum of the NN 3 center is revealed without the interference from the spectra of other higher energy centers.This investigation offers a direct proof for that all the phonon replicas are the phonon sidebands governed by the Huang Rhys’ multiphonon optical transition theory.

Resonant Raman Scattering and Photoluminescence Emissions from Above Bandgap Levels in Dilute GaAsN Alloys

The transitions of E0 ,E0 ＋A0, and E＋ in dilute GaAs（1-x） Nx alloys with x = 0.10% ,0.22% ,0.36% ,and 0.62% are observed by micro-photoluminescence. Resonant Raman scattering results further confirm that they are from the intrinsic emissions in the studied dilute GaAsN alloys rather than some localized exciton emissions in the GaAsN alloys. The results show that the nitrogen-induced E E＋ and E0 ＋ A0 transitions in GaAsN alloys intersect at a nitrogen content of about 0.16%. It is demonstrated that a small amount of isoelectronic doping combined with micro-photoluminescence allows direct observation of above band gap transitions that are not usually accessible in photoluminescence.

苯及其含氮等电子体化合物的结构和性质的理论研究

采用密度泛函理论的B3LYP方法在aug-cc-pvDZ基组上研究了13种苯及其含氮等电子体化合物的分子结构、能量和异构体相对稳定性,重点考察了含氮量对化合物含能性质的影响.结果表明:随着氮原子数增加分子的总能量降低,且存在很好的线性相关性.采用G3方法对分子的生成热进行了计算,结果显示随着分子中氮原子个数增加,各含氮等电子体化合物的生成热将增大,其中六嗪、五嗪的生成热较大,它们成为含能材料的潜力较大.对各异构体分析显示,氮原子位置与总能量和生成热的关系均为:(邻)间位<(邻)对位<邻位.此外,通过NBO方法分析了分子的超共轭作用和立体排斥能对异构体稳定性的影响,结果表明超共轭作用是影响各异构体构型相对稳定性的主要因素.

神光Ⅱ黑腔等离子体时间分辨的电子温度诊断

在神光Ⅱ强激光装置上,用条纹晶体谱仪对埋点于黑腔靶内壁上的双示踪Ti和Cr材料的激光等离子体高离化态离子发射的X射线谱线进行实验测量,获得超高时间分辨的X射线细致结构谱线。用碰撞辐射模型计算了非局域热动平衡的等离子体布居数,组态平均速率系数由一级微扰理论计算,电子波函数由Hartree-Fock Slater自洽场方法计算,给出了Ti和Cr激光等离子体在电子密度为1019~1022cm-3范围内的He-α线强比与电子温度的关系曲线。采用等电子X射线谱线法,获得了黑腔靶激光等离子体冕区的电子温度随激光脉冲加热从低温到高温、然后缓慢下降的演化过程,其峰值达到2.05 keV。

高离化态离子能级一般拟合公式的提出及研究

分析Ｊ．－Ｆ．Ｗｙａｒｔ和Ｉ．Ｍａｔｓｕｓｈｉｍａ等人提出的拟合公式，考虑高Ｚ离子的量子电动力学效应，综合提出能级的一般拟合公式：ΔＥ＝Ａ＋ＢＺＣ＋ＣＺ２Ｃ＋ＤＺ３Ｃ＋ＥＺ４Ｃ＋ＦＺ５Ｃ＋ＧＺ６Ｃ＋ＨＥ７Ｃ＋Ｈｉｇｈｅｒｏｒｄｅｒｔｅｒｍｓ。并以类Ｎｉ为例探讨了此公式的完善性和合理性。

十二烷基甜菜碱的界面活性及其体系的相态研究

合成了十二烷基甜菜碱（Ｃ１２ＢＥ），经提纯得到合格的样品，测定其等电点为ｐＨ＝４．９。ｐＨ＜４．９，分子带正电；ｐＨ≥４．９，分子呈电中性。研究ｐＨ值对其界面活性的影响，同时还研究了醇的种类、浓度，水的盐度、ｐＨ值等因素对Ｃ１２ＢＥ／醇／水／油体系相态的影响，得到了中相微乳液的特性参数。其中有关ｐＨ对相态的影响的研究很有特点。

RbⅧ—NbⅫ离子n=4complex跃迁谱线、波长和振子强度

用HXR方法计算了类锌等电子序列RbⅧ—NbⅫ离子n =4complex组态能级。通过对各能级值沿等电子序列的变化规律分析 ,找出了ΔE随Zc 变化的一种新的拟合公式 ,运用此公式和我们自己设计的FOR TRAN程序对上述组态各能级值进行了系统的拟合计算。给出了 4s2 4s4 p ,4s4 p 4s4d 跃迁谱线波长和相应的振子强度。

静压下ZnS∶Te中Te等电子陷阱的发光

研究了 4块ZnS∶Te薄膜样品 (Te组分从 0 .5 %到 3.1% )的光致发光谱在常压下的温度特性 .对于Te组分较小的 2块样品观察到 2个发光峰 ,分别来自Te1和Te2 等电子陷阱 ;而对Te组分较大的 2块样品则只观察到 1个来自Te2 等电子陷阱的发光 .我们还研究了这些发光峰在低温 15K下的流体静压压力行为 .观察到与Te1有关的发光峰压力系数比ZnS带边的要大很多 ,而与Te2 有关的发光峰压力系数则比带边小 .根据Koster Slater模型 ,价带态密度半宽随压力的增加是Te1中心有较大压力系数的主要原因 ,而Te1和Te2

酶蛋白分子可及性与等电点关系的研究

依据酶的晶体结构数据对它的分子可及性进行了计算和分析 ,探讨了氨基酸可及性与酶性质的关系 ,研究了氨基酸可及性和酶等电点之间的关系 ,发现了氨基酸可及性与酶等电点之间的线性关系。

类镍序列3d^94s，3d^94p，3d^94d组态原子参数的计算

用多组态自洽场方法，结合我们提出的半经验拟合公式，系统计算了类镍等电子序列ＮｉⅠＸｅⅩⅩⅦ离子３ｄ９４ｓ，３ｄ９４ｐ，３ｄ９４ｄ组态的能级、波长和振子强度。