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.     

Computational study of reactivity and solubility of Rubescin D and E molecules in gas phase and in solvent media using Hartree-Fock and DFT methods

The quantum chemical methods were used to study the global and local reactivity, the energy and free energy of solvation, the partition coefficient and the solubility of Rubescin D and E in gas phase and some solvents media using the IEF-PCM model. The analysis of energy and free energy of solvation shows that the molecules are thermodynamically more stable in water. The values of electrophilicity index, chemical potential, hardness and maximum charge transfer indexes have revealed that both molecules can react easily in water. C₂ and C₆₂; C₅₇ and C₃₂; are preferred site for electrophilic and free radical attack. The log P values show that Rubescin D and E are lipophilic and can be delivered orally. The log S values are also calculated and found to be in the range of -1 to -5 at all the levels used.     

Reactivity of phenyl N‐phenylcarbamates in the alkaline hydrolysis reaction

In the present study, we explore the application of several theoretically estimated indices that characterize the reactivity of a series of phenyl N‐phenylcarbamates in the alkaline hydrolysis reaction. The rate constants (at 25 °C) for the hydrolysis of several derivatives were spectrophotometrically determined. The obtained kinetic data in this study, combined with literature data for other derivatives, were then correlated with theoretically estimated reactivity indices: Hirshfeld and NBO atomic charges, the Parr electrophilicity index (ω), and the electrostatic potential at the carbon and oxygen atoms of the reaction centre (V_C, V_O). The predictive ability of these quantities is discussed in a comparative context. Copyright © 2011 John Wiley & Sons, Ltd.     

Substituent effects in the Diels–Alder reactions of butadienes,cyclopentadienes, furans and pyroles with maleic anhydride

In this study, activation energies in the Diels–Alder reactions of a series of substituted butadienes, cyclopentadienes, furans and pyroles with maleic anhydride were calculated by the M06‐2X/6‐31G(d) method. The substituent effects on the reactivity and the endo–exo selectivity have been examined. The strength of reactivity effect has an order of pyroles > furans > cyclopentadienes > butadienes, which is highly correlated with the lowest unoccupied molecular orbital energy, the electronic chemical potential and the electrophilicity of parent diene but relatively less correlated with the highest occupied molecular orbital energy and chemical hardness. The trend that an increase of necleophilicity caused by an electron‐donating group on the diene favors the endo TS is effective with C2 substitution. With C1 substitution, the trend is ambiguous or even opposite. Copyright © 2015 John Wiley & Sons, Ltd.     

Theoretical analysis on structural,spectroscopic, and electronic properties of some 2-aminobenzimidazole complexes by using PBE1PBE,B3LYP,and HF methods

The molecular geometry, vibrational frequencies, gauge including atomic orbital (GIAO) ¹H and ¹³C chemical shift values of ABZ-TNB [ABZ-TNB: 2-aminobenzimidazole-trinitrobenzene] and ABZ-PA [ABZ-PA: 2-aminobenzimidazole-picric acid] in the ground state were calculated by using density functionals (B3LYP and PBE1PBE) and Hartree-Fock (HF) methods with the 6–31 ++ G(d,p) basis set. Furthermore, the electronic spectrum of title complexes was calculated with the time dependent DFT levels (TD-PBE1PBE and TD-B3LYP) and HF (TD-HF) method starting from the ground state geometry optimized in the gas phase. A detailed assignment of vibrational spectra was made on the basis of the calculated potential energy distribution (PED). Total static dipole moment (μ), the mean polarizability (〈α〉), the anisotropy of the polarizability (Δα), the mean first-order hyperpolarizability (〈β〉), highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies, chemical hardness (η) and electronegativity (χ) of ABZ-TNB and ABZ-PA complexes were also investigated with quantum chemical calculations. Additionally, data obtained from quantum chemical calculations were compared with the experimental ones.     

13C NMR and Fukui function analysis on C82 hydroxylated fullerene through density functional theory

Density functional theory calculations were performed on C₈₂ hydroxylated fullerene. B3LYP and PBE0 functionals with 6-31G** basis set were utilised to get chemical shieldings, chemical shifts and the isotropic Fermi contact coupling on each atomic site. A relation between nuclear magnetic resonance (NMR) properties and reactivity of the molecule, obtained through the electronic Fukui function, was observed. Interestingly, the most stable configurations of OH groups adsorbed on C₈₂ surface were obtained when the hydroxyl groups are adsorbed on deshielded (isotropically and anisotropically) sites. For open-shell systems, a relation between isotropic Fermi contact, spin density and average Fukui function was found, that is, sites with a great amount of Fukui function (analytical and the one obtained through finite difference) and spin density have the largest isotropic Fermi contact coupling data. With the adsorption of the first hydroxyl molecules, spin densities and Fukui functions show preferential sites to adsorb the following OH groups close to previously adsorbed. Additionally, theoretical spectra of chemical shifts of C₈₂(OH)_n (n = 1, 2, 3 and 4) were obtained and they were compared with experimental reports, getting a reasonable comparison. For example, regarding ¹³C NMR chemical shifts obtained in C₈₂OH molecule, 80 ppm (B3LYP) and 79 ppm (PBE0) were calculated on hydroxylated carbon, which is in good agreement with experimental results in C₆₀ fullerols.     

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.     

Pd nanoparticle-mediated acetone sensing performance improvement of SnO2 substrate: A combined DFT and experimental study

The article presents a combined theoretical and experimental study attempting to show how Pd nanoparticles (NPs) loading onto SnO₂ substrate improves the acetone gas sensing performance. Pristine nanostructured SnO₂ and Pd nanoparticles (Pd NPs) loaded SnO₂ substrates have been prepared, characterized, and their acetone sensing performances have been measured. Experimental measurements have shown that Pd NP loading onto SnO₂ suppresses the interfering effects of ethanol, water vapors, etc., and enhances the acetone sensor response, reversibility, response/recovery speeds, and signal-to-noise ratio. Various parameters like the adsorption energy, HOMO–LUMO energy gap, charge distribution, polarizability change, electrophilicity index, global hardness, etc., of several model systems, have been computed by using DFT. The computed parameters have been correlated with the conductivity, local reactivity, sensor response and selectivity, response/recovery times, etc., of the systems to understand the molecular-level effects of the Pd NP loading onto the SnO₂ on the gas sensing process.     

密度泛函理论研究ScnO(n=1—9)团簇的结构、稳定性与电子性质

采用基于密度泛函理论的BP86/CEP-121G （O原子采用6-311G^**基组）方法,对Sc_nO （n=1—9）团簇的几何结构、能量与稳定性、电子结构性质及其随团簇尺寸的变化趋势进行了研究.随着团簇原子个数的增加,O原子从位于Sc_n团簇结构的边缘转变为占据团簇的内部位置.O原子的掺入增加了Sc_n团簇的稳定性,使其能隙升高,并改变了其稳定性及电子结构性质随团簇尺寸变化的规律;含有偶数个Sc原子的氧化物团簇比其周围邻近的含有奇数个Sc原子的氧化物团簇具有相对较高的稳定性.Sc_nO团簇电离势的理论计算值与实验值符合得较好,而其电子亲和势呈现振荡交替上升的变化趋势;用最大化学硬度规律等方法表征了Sc_nO氧化物团簇的稳定性和电子结构性质. 关键词： nO团簇')" href="#">Sc_nO团簇 几何结构 电子性质 密度泛函理论     

Control of dissipation of energy via reservoirs of coherent states

Dynamic profiles of various chemical reactivity indices like chemical potential, chemical hardness, electrophilicity, susceptibility, etc., within a confined environment during the interaction of atoms with strong oscillating time dependent magnetic fields have been studied. In the present study hydrogen and helium atoms in ground state (n = 1), as well as in excited state (n = 20) are considered. Time-dependent Schrödinger equations are solved for the ground and excited states of hydrogen atom and the Rydberg state of the helium atom while a generalized nonlinear Schrödinger equation is solved for the ground state of the helium atom. Dirichlet type boundary condition has been used to implement confinement to the systems. With an increase in the degree of confinement the system gets harder and hence becomes more stable. Keeping the confinement radius fixed, systems get more stabilized in strong field compared to weak field.     

The structure and the potential energy function of AlSO(C_S,X~2A″)

By using the B3P86/aug-cc-pvtz method,the accurate equilibrium geometry of the AlSO(CS,X2A″) molecule has been calculated and compared with available theoretical values.The obtained results show that the AlSO molecule has a most stable structure with bond lengths of R OAl = 0.1864 nm,R OS = 0.1623 nm,R AlS = 0.2450 nm,together with a dissociation energy of 13.88 eV.The possible electronic states and their reasonable dissociation limits for the ground state of the AlSO molecule were determined based on the principle of atomic and molecular reaction statics.The analytic potential energy function of the AlSO molecule was derived by the many-body expansion theory and the contour lines were constructed for the first time,which show the internal information of the AlSO molecule,including the equilibrium structure and stable point.The analysis demonstrates that the obtained potential energy function of AlSO is reasonable and successful and the present investigations provide important insights for further study on molecular reaction dynamics.     

Numerical Simulations of femtosecond-laser-induced dynamic alignment of molecules in the high-frequency off-resonance regime

The motion equation for ? between the molecular axis and laser polarization direction in a high-frequency off-resonance femtosecond laser field is deduced while simultaneously examining the effects of a permanent dipole moment and field-induced polarizability and hyperpolarizability to molecular rotation. Femtosecond-laser-induced dynamic alignment of CO, N₂, and Br₂ molecules are investigated by numerically solving the obtained rotation equation for the angle ?. The effects of the molecular permanent dipole moment and the field-induced polarizability and hyperpolarizability on the degree of alignment are presented at different intensities. Our computational results show that the dynamic alignment of molecules is primarily determined by field-induced polarizability and the second hyperpolarizability for the laser intensity range from 5 × 10¹⁴ to 5 × 10¹⁶ W/cm². The contributions of higher order correction terms to molecular alignment can usually be neglected. The polarizability-field interaction makes the angular distributions of a molecule have a maximum along the polarization axis and a minimum perpendicular to it. The role of the second hyperpolarizability keeps the molecular counts maximum along the laser polarization direction but minimum at an angle of 45° between the molecular axis and the polarization direction. There is also a second maximum of molecular counts perpendicular to the polarization axis. For CO, N₂, and Br₂ molecules, the dependences of laser-induced dynamic alignment on laser intensity exhibit completely different characteristics.     

Partitioning Entropy with Action Mechanics: Predicting Chemical Reaction Rates and Gaseous Equilibria of Reactions of Hydrogen from Molecular Properties

Our intention is to provide easy methods for estimating entropy and chemical potentials for gas phase reactions. Clausius’ virial theorem set a basis for relating kinetic energy in a body of independent material particles to its potential energy, pointing to their complementary role with respect to the second law of maximum entropy. Based on this partitioning of thermal energy as sensible heat and also as a latent heat or field potential energy, in action mechanics we express the entropy of ideal gases as a capacity factor for enthalpy plus the configurational work to sustain the relative translational, rotational, and vibrational action. This yields algorithms for estimating chemical reaction rates and positions of equilibrium. All properties of state including entropy, work potential as Helmholtz and Gibbs energies, and activated transition state reaction rates can be estimated, using easily accessible molecular properties, such as atomic weights, bond lengths, moments of inertia, and vibrational frequencies. We conclude that the large molecular size of many enzymes may catalyze reaction rates because of their large radial inertia as colloidal particles, maximising action states by impulsive collisions. Understanding how Clausius’ virial theorem justifies partitioning between thermal and statistical properties of entropy, yielding a more complete view of the second law’s evolutionary nature and the principle of maximum entropy. The ease of performing these operations is illustrated with three important chemical gas phase reactions: the reversible dissociation of hydrogen molecules, lysis of water to hydrogen and oxygen, and the reversible formation of ammonia from nitrogen and hydrogen. Employing the ergal also introduced by Clausius to define the reversible internal work overcoming molecular interactions plus the configurational work of change in Gibbs energy, often neglected; this may provide a practical guide for managing industrial processes and risk in climate change at the global scale. The concepts developed should also have value as novel methods for the instruction of senior students.     

The HSAB principle as a means to interpret the reactivity of carbon nanotubes

Polycyclic curved aromatic fragments (C₂₄H₁₂) have been employed as models of the single-walled carbon nanotubes (n,0), where n varies from 4 up to 30. Those structures were chosen on the basis of the analysis of the strain energy values calculated for the models possessing various sizes. The flat coronene structure has been chosen as a molecular fragment topologically resembling the honeycomb lattice in order to investigate the relation between the curvature and reactivity of the sidewalls of SWNTs. In the current study we took into account the interaction of CO and NH₂ (treated as probe molecules) with the exterior surface of nanotubes. Obtained results illustrate that both total as well as local hardness and/or molecular electrostatic potential (MEP) can be a good measure for the reactivity if the influence of geometrical changes is considered. The systematic theoretical studies also show that the calculated interaction energies of sorbed CO on those models are related to the both types of hardness. On the other hand, in the case of amidogen sorbed on the nanotube surface the correlation between the binding energy and MEP is visible. Those differences can be explained by various kinds of the adsorption mechanism, i.e. physical or chemical adsorption, respectively.     

Density functional theory and molecular dynamics simulation study on corrosion inhibition performance of mild steel by mercapto-quinoline Schiff base corrosion inhibitor

Corrosion inhibition mechanism of two mercapto-quinoline Schiff bases, eg., 3-((phenylimino)methyl)quinoline-2-thiol (PMQ) and 3-((5-methylthiazol-2-ylimino)methyl) quinoline-2-thiol (MMQT) on mild steel surface is investigated by quantum chemical calculation and molecular dynamics simulation. Quantum chemical parameters such as E_HOMO, E_LUMO, energy gap (ΔE), dipolemoment (µ), electronegativity (χ), global hardness (η) and fraction of electron transfers from the inhibitor molecule to the metallic atom surface (ΔN) have been studied to investigate their relative corrosion inhibition performance. Parameters like local reactive sites of the present molecule have been analyzed through Fukui indices. Moreover, adsorption behavior of the inhibitor molecules on Fe (1 1 0) surface have been analyzed using molecular dynamics simulation. The binding strength of the concerned inhibitor molecules on mild steel surface follows the order MMQT>PMQ, which is in good agreement with the experimentally determined inhibition efficiencies. In view of the above, our approach will be helpful for quick prediction of a potential inhibitor from a lot of similar inhibitors and subsequently in their rational designed synthesis for corrosion inhibition application following a wet chemical synthetic route.     

Optical properties and upconversion in Yb3+—Tm3+ co-doped oxyfluoride glasses and glass ceramics

A theoretical study has explored the changes brought upon the electron density of the open (C_2v) and cyclic (D_3h) forms of ozone by protonation. Although protonation results in a strong deformation of the electron density of ozone with notably different charge distributions for the stable forms of O₃H⁺, the electric dipole polarizability is almost stable for the open protonated species. The polarizability of the cyclic form is less affected by protonation than that of the open one. The anisotropy of the dipole polarizability discriminates very clearly between open and closed protonated ozone. We expect the present findings to advance our understanding of the chemical reactivity of O₃H⁺.     

Pressure and temperature dependences of the dielectric constant,Raman spectra and lattice constant of SnI42

The pressure and temperature dependences of the Raman frequencies, static dielectric constant and lattice constant of the molecular crystal SnI₄, were investigated. These results are combined to evaluate the pure volume and pure temperature (i.e. volume-independent) dependences of the molecular polarizability and of the Raman-active phonon self-energies. The pressure results also allow the separation of the Raman modes into external and internal modes of the crystal; the external modes exhibit a much stronger pressure dependence, and thereby larger Grüneisen parameters, than do the internal modes. The Raman frequencies increase (decrease) with increasing pressure (temperature) whereas the dielectric constant increases with both increasing pressure and temperature, emphasizing the importance of non-volume effects. In fact, it is found that the isobaric temperature dependence of the dielectric constant is dominated by the pure temperature dependence of the molecular polarizability. The pure volume dependence of the polarizability, on the other hand, is relatively small as is perhaps typical of most molecular crystals.