Study of effective hardness and condensed Fukui functions using AIM,ab initio,and DFT methods

The effective chemical hardness for some triatomic molecules has been studied using the ‘atom in a molecule’ approach (AIM). Molecular chemical hardness values calculated from the effective chemical hardness of individual atoms agree with experimental and theoretically calculated molecular hardness values. Condensed Fukui functions have been calculated using Mulliken, NPA and AIM charges calculated by HF and B3LYP methods using the 6-31+G** basis set. All population schemes have predicted few negative Fukui functions, which correlate well with effective chemical hardness values.     

非链式脉冲DF化学激光器反应动力学模型

依据非链式脉冲氟化氘(DF)激光器的反应机理, 采用速率方程理论, 综合考虑了基态DF分子、D₂分子、D原子、F原子对激发态DF分子的消激发作用, 建立了非链式脉冲DF激光器反应动力学模型. 运用Runge-Kutta法对该模型进行数值计算, 得到了增益区内各组分粒子数密度随时间的变化关系. 进而运用该模型研究了工作气体配比和输出镜反射率对DF激光器腔内光子数密度、 单脉冲能量、脉冲宽度和输出功率的影响, 得到了最佳气体配比和最佳输出镜反射率参数. 采用放电引发方式对非链式DF激光器进行了实验研究, 实验测得脉冲波形及单脉冲能量与速率方程理论模型计算结果基本一致. 本文的研究结果可为非链式脉冲DF激光器的优化设计提供理论参考. 关键词： 脉冲DF激光器 动力学模型 速率方程 数值计算     

Determination of effective atomic charge,extra-atomic relaxation and madelung energy in chemical compounds on the basis of X-ray photoelectron and auger transition energies

A new method is proposed for the determination of effective atomic charge, extra-atomic relaxation, and Madelung energy in chemical compounds, based on the experimentally measured energies of X-ray photoelectron and Auger transitions. The method has been applied to solid compounds of the elements from Na to Cl, and to a number of free sulfur-, phosphorus-, silicon-, and chlorine-containing molecules. The experimental energies are represented as consisting of two parts. The first part is determined by the ionization energy of a free ion with a given effective charge, and includes the intra-atomic relaxation. The second part is determined by the Madelung energy and the extra-atomic relaxation. The first contribution is calculated by using the Hartree-Fock method. The effective atomic charges required have been found from the shifts of Kα-lines in the X-ray spectra. The extra-atomic relaxations are obtained as the differences between experimental and theoretical Auger parameters, and the values calculated are the additive functions of ligands of the atom studied. The increments of the additive scheme correlate with the ligand refractions. The effective charges, extra-atomic relaxation energies and Madelung potentials obtained from ESCA and AES data agree well with both calculated and direct experimental results.     

Equations of state and phase diagrams of hydrogen isotopes

A new form of the semiempirical equation of state proposed for the liquid phase of hydrogen isotopes is based on the assumption that its structure is formed by cells some of which contain hydrogen molecules and others contain hydrogen atoms. The values of parameters in the equations of state of the solid (molecular and atomic) phases as well as of the liquid phase of hydrogen isotopes (protium and deuterium) are determined. Phase diagrams, shock adiabats, isentropes, isotherms, and the electrical conductivity of compressed hydrogen are calculated. Comparison of the results of calculations with available experimental data in a wide pressure range demonstrates satisfactory coincidence.     

An alternative approach on the calculation of cohesive energy density and isothermal compressibility of alkali metal halides

In the present paper, new and useful theoretical methods for the estimation of cohesive energy density (Ced) and isothermal compressibility (k_T) of alkali metal halides are described. The mentioned theoretical methods include the use of Kaya molecular hardness equation published by us in recent years. Cohesive energy density and isothermal compressibility of alkali metal halides were calculated in the framework of mentioned theoretical methods and the results obtained were compared with both experimental data and the results of previous theoretical methods proposed to calculate the aforementioned quantities, namely cohesive energy density and isothermal compressibility. It is important to note that the results obtained in the study are in good agreement with the available experimental data and with the results of previous theoretical methods. Additionally, we also investigated the correlation with lattice energy of cohesive energy density and isothermal compressibility for alkali halides.     

Hartree-Fock and density functional theory studies on ionization and fragmentation of halomethane molecules by positron impact

The fragmentation patterns of halomethane molecules CF₄, CCl₂F₂, CClF₃ and CHF₃ due to positron impact have been studied by using ab initio and density functional theory (DFT) methods. The geometries of parent molecules and fragments are optimized at HF, MP2 and B3LYP levels of theory using the 6–31+G(d, p) basis set. The calculated reaction energies agree with the experimental values. The condensed Fukui functions have been calculated using the atomic charges of the Mulliken population analysis (MPA) scheme for the halomethane molecules. The calculated condensed Fukui functions successfully predict the reactive site of the halomethane molecules for the positron, electron and radical attacks. The chemical hardness and chemical potential for the above molecules and its fragments are calculated.     

Improving amplitude-modulated signals by re-scaled and twice sampling vibrational resonance methods

Quantum chemical calculations have been employed to study the molecular effects produced by \(\hbox {Cr}_{2}\hbox {O}_{3}/\hbox {SnO}_{2}\) optimised structure. The theoretical parameters of the transparent conducting metal oxides were calculated using DFT / B3LYP / LANL2DZ method. The optimised bond parameters such as bond lengths, bond angles and dihedral angles were calculated using the same theory. The non-linear optical property of the title compound was calculated using first-order hyperpolarisability calculation. The calculated HOMO–LUMO analysis explains the charge transfer interaction between the molecule. In addition, MEP and Mulliken atomic charges were also calculated and analysed.     

Chemical hardness-based prediction of the surface tension and enthalpy changes of sublimation for alkali halides

A new theoretical route employing the concept of chemical hardness has been developed to predict the surface tension γ and the changes of the standard enthalpies (CSEs) of sublimation Δ_sH⁰ of alkali halides. The values of these quantities have been calculated by means of the ratios η_M/V^1/3_m where η_M and V_m are the molecular hardness and molecular volume, respectively. The obtained results have been compared with those of previous theoretical models as well as with experimental data.     

Relativistic gravitation

Classical dynamics, often called 'molecular dynamics' when applied to atoms and molecules, is much easier than solving the many-body Schrodinger equation for a number of reasons. In particular, correlation and rearrangement are simple in classical dynamics. Fermion molecular dynamics (FMD) is a quasi-classical method for treating quantum-mechanical systems using classical equations of motion with momentum-dependent model potentials added to the usual Hamiltonian. These model potentials constrain the motion to satisfy the Heisenberg uncertainty and the Pauli exclusion principles. We discuss the foundations of the FMD model and its applications to atomic and molecular structure, ion-atom collisions, stopping powers, formation of antiprotonic atoms, and multiple ionization of atoms in strong laser fields.     

Application of the nuclear liquid drop model to atomic and molecular physics problems

The liquid drop model is applied to describe some basic properties of atoms, homoatomic molecules, metallic clusters of atoms and fullerene molecules. Equilibrium atomic size, energy and polarizability of the atom are calculated. Collective modes of oscillations (dipole, quadrupole and monopole, or breathing, ones) are regarded. Electromagnetic radiation by an atom, passing through a barrier is studied. Equilibrium volume of a homoatomic molecule of two atoms, axes ratio, dissociation energy and the frequencies of the dipole oscillations are calculated. Models to describe some properties of clusters and fullerene molecules are proposed. The size of the metallic cluster, its energy and the frequency of dipole oscillations are calculated. The frequencies of the dipole and breathing mode oscillations of the fullerene molecules are obtained. The calculated frequency of the dipole oscillations was found to be in a rather good accord with the experimental one.     

Spectroscopic evaluation of the global hardness of the atoms

This study explored a new route for calculating the global hardness of atoms using spectroscopy. Working on a new definition of global hardness and relying on the Bohr model of the hydrogenic atom, a new formula for the global hardness of atoms was derived in terms of the wave number, reflecting the electron transition from the ground state to infinity. Since the spectral lines emitted from an atom bear the signature of all complex and complicated energetic effects, including relativity, in the internal constitution of the atom, it is expected that all such effects are automatically subsumed in the hardness data computed in terms of spectral lines. The hardness of the atoms of the 103 elements of the periodic table have been computed using spectral data and in terms of the new formula suggested in this work. The effect of relativity in pre- and post-lanthanoid elements is distinctly manifest. The express periodic behaviour and correlation of the most important physico-chemical properties of elements suggest that the present approach is an alternative scientifically meaningful method for evaluating the global hardness of atoms.     

Effect of substituent on UV–visible absorption and photostability of liquid crystals: DFT study

The electronic transitions in the ultraviolet–visible (UV–Vis) range of two nematogens, namely 4′-cyanophenyl-4-n-pentylbenzoate and 4′-cyanophenyl-4-n-pentoxybenzoate, have been studied. The UV–Vis and circular dichroism spectra of these molecules have been simulated using the TDDFT/B3LYP/6-31+G(d) method. Mulliken atomic charges for each molecule have been compared with Loewdin atomic charges to analyze the molecular charge distribution and phase stability. The highest occupied molecular orbital and lowest unoccupied molecular orbital energies corresponding to the electronic transitions in the UV–Vis range have been reported. The excited states have been calculated via configuration interaction singles with semi-empirical Hamiltonian ZINDO (Zerner's intermediate neglect of differential overlap method). Further, the effect of substituent on ultraviolet absorption and photostability of the molecules has been discussed. The photostability of the molecules has been investigated in order to understand the application and operation with ultraviolet and visible light regions.     

Semiempirical studies of core electron binding energies Part II. SCC-MO Calculations for uracil and its derivatives

The solid-state binding energies of uracil and some of its derivatives have been calculated using semiempirical SCC-MO intramolecular potential expressed in the pointcharge approximation. The results are essentially in satisfactory agreement with experimental data, giving at the same time a simple and transparent interpretation of the ESCA spectra which is close to that suggested by chemical intuition. Splitting of some unresolved N 1 s peaks is proposed, and separate binding energies are attributed to particular nitrogen atoms. The relaxation energies are discussed briefly. The present and earlier evidence indicates that formal atomic charges are meaningful within the theoretical framework adopted, despite the fact that they cannot be defined in a unique fashion.     

A quantum-chemical study of spectral and luminescent properties of some molecules belonging to the 8-azasteroid class

The spectral and luminescent properties of two molecules belonging to the 8-azasteroid class were considered using the method of partial neglect of differential overlap (PNDO). The geometries of the absorbing and fluorescing conformers were selected and the absorption spectra of the studied molecular structures were interpreted. The cause of the low quantum yield of fluorescence from the base molecule and the mechanism of the effect of substitution by the methoxy groups on this yield are established. Calculations of molecular electrostatic potential were performed using the wave functions obtained by the PNDO method; the results show that the proton-acceptor properties of the unsubstituted molecule are controlled by the oxygen atoms of CO groups in the case of both conformers; in the equilibrium geometry of the fluorescing conformer, a nitrogen atom is added to oxygen atoms, although the acceptor properties of this atom are less pronounced than those of oxygen atoms.     

The role of the electrostatic interaction in shifting the vibrational frequencies for two adsorbed molecules

We use a simple model to compute the shift of the vibrational frequencies of two adsorbed molecules as a function of inter-molecular distance, and various molecular and metal parameters. We assume that the atoms posses static and dynamic charges and the molecule has an electronic polarizability. The chemical bonds are described by Morse potentials. The electrostatic interactions are computed by a density functional method. We conclude that the use of vibrating point dipoles and of the image theorem in such calculations is an oversimplification.     

Molecular structure, spectroscopic properties and DFT calculations of 2-(methylthio)nicotinic acid

The analyses of possible conformations, molecular structures, vibrational and electronic properties of 2-(methylthio)nicotinic acid molecule, C₇H₇NO₂S, with the synonym 2-(methylsulfanyl)nicotinic acid have been first presented theoretically. At the same time, FT-IR and micro-Raman spectra of 2-(methylthio)nicotinic acid were recorded in the regions 400–4000 cm^?1 and 100–4000 cm^?1, respectively. In our calculations, the DFTB3LYP method with 6–311G(d, p) basis set was used to have the structural and spectroscopic data about the mentioned molecule in the ground state and the results obtained were compared with experimental values. Furthermore, gauge invariant atomic orbital (GIAO) ¹H and ¹³C NMR chemical shifts in different solvents, UV-vis TD-DFT calculations, the highest occupied molecular orbitals (HOMO-2, HOMO-1, HOMO), lowest unoccupied molecular orbital (LUMO), molecular electrostatic potantial (MEP) surface, atomic charges and thermodynamic properties of molecule have been theoretically verified and simulated at the mentioned level. The energetic behavior of title molecule in different solvent media was investigated by using DFT/B3LYP method with 6–311G(d, p) basis set in terms of integral equation formalism polarizable continuum model (IEFPCM). In addition, the calculated infrared intensities, Raman activities, reduce masses and force constants of the compound under study have been also reported.     

New results in above-threshold ionization and high-order harmonic generation of atomic and molecular systems

Numerical results obtained applying the strong-field approximation to atomic and molecular processes in intense laser fields are presented. In particular, the forward-backward asymmetry in high-order above-threshold ionization (HATI) of Ar atoms by a few-cycle laser pulse is considered. It is shown that the resonantlike enhancements observed in the focal-averaged spectra disappear with the decreasing laser pulse duration. For HATI and high-order harmonic generation (HHG) by molecular systems, we present new results for diatomic molecules. The choice of gauge and the problem of dressing of the initial bound state are discussed. The appearance of the interference minima in molecular HATI and HHG spectra and their role in the characterization of the molecular structure are considered using the example of the Ar₂ molecule.     

Quantum microscopic vs. classical macroscopic calculations on the phenomenon of electrostatic influence

In order to compare microscopic and macroscopic approaches to the phenomenon of electrostatic influence, we have studied the atomic charges of an electric conductor, obtained either from macroscopic classical electrostatics, or microscopic quantum ab initio calculations. A torus was chosen as conducting material, built from valence monoelectronic atoms and influenced by an external point charge. The classical electric charges are obtained by integrating the macroscopic density over “atomic" sectors. This density is determined from a numerical integration of linearized electrostatic equations. The quantum charges are defined from Natural Orbitals in MP2/6-31G* calculations on clusters of different sizes. The overall agreement is good, with reasonable discrepancies due (i) to the continuity of the macroscopic model, which ignores the oscillations on atomic distances; and (ii) to the linearity constraint in the macroscopic equations.