Factors affecting the strengths of σ-hole electrostatic potentials

A σ-hole is a region of diminished electronic density on the extension of a covalent bond to an atom. This region often exhibits a positive electrostatic potential, which allows attractive noncovalent interactions with negative sites. In this study, we have systematically examined the dependence of σ-hole potentials upon (a) the atom having the σ-hole, and (b) the remainder of the molecule. We demonstrate that not only relative electron-attracting powers need to be considered, but also relative charge capacities (or polarizabilities), and that other factors can also have significant roles.     

Nonlinear optical properties of C<Subscript>60</Subscript> with explicit time-dependent electron dynamics

An explicit electron dynamics approach has been used to calculate the nonlinear optical properties of C₆₀ and its radical anion. An external perturbation, in the form of an oscillating electric field, induces the time-evolution of the molecular wavefunction. The time-averaged instantaneous dipole moment of the systems gives the molecular response to perturbations of varying field intensities and frequency of oscillation. The polarizabilities and the second-order hyperpolarizabilties have been calculated and are in good qualitative agreement with experimentally available data. In line with previous theoretical and experimental studies, the nonlinear effect is enhanced for the radical species. Contribution to the Fernando Bernardi Memorial Issue.     

Blackbody radiation shift of the Al<Superscript>+</Superscript> clock transition

The blackbody radiation shift of the Al⁺ 3s^{2 1}S^e ₀ ↦ 3s3p ³P^○ ₀ clock transition is evaluated. The polarizabilities of the two states are determined by means of configuration interaction calculations in conjunction with oscillator strength sum rules. The ground state polarizability was 24.14 ±0.12 a.u. while the metastable state polarizability was 24.62 ±0.25 a.u. The derived frequency shift at 300 K was Δν= -0.0042 ±0.0032 Hz. Some auxiliary sum rules are evaluated that allow for the conversion of a finite frequency polarizability difference to a static polarizability difference.     

Infrared optical constants, dielectric constants, molar polarizabilities, transition moments, dipole moment derivatives and Raman spectrum of liquid cyclohexane

Previous studies have been done in this laboratory focusing on the optical properties of several liquid aromatic and aliphatic hydrocarbons in the infrared. The current study reports the infrared and absorption Raman spectra of liquid cyclohexane. Infrared spectra were recorded at 25 °C over a wavenumber range of 7400–490 cm⁻¹. Infrared measurements were taken using transmission cells with pathlengths ranging from 3 to 5000 μm. Raman spectra were recorded between 3700 and 100 cm⁻¹ at 25 °C using a 180° reflection geometry. Ab initio calculations of the vibrational wavenumbers at the B3LYP/6311G level of theory were performed and used to help assign the observed IR and Raman spectra. Extensive assignments of the fundamentals and binary combinations observed in the infrared imaginary molar polarizability spectrum are reported. The imaginary molar polarizability spectrum was curve fitted to separate the intensity from the various transitions and used to determine the transition moments and magnitudes of the derivatives of the dipole moment with respect to the normal coordinates for the fundamentals.     

Debye屏蔽势下的Na原子

结合自由Na原子的l-依赖模型势, 采用B-样条基组展开方法计算了等离子体环境中Na原子的的基态能量、振子强度、偶极极化率、四极极化率、八极极化率等随Debye长度的变化. 其中原子的等离子体效应采用Debye屏蔽模型. 计算结果与其他研究者的结果符合得很好; 在Debye屏蔽等离子体环境下下基态能量的结果与Sahoo [Sahoo S Ho Y K 2006 Phys. Plasmas 13, 063301]和Li [Li H W and Kar S, 2012 Phys. Plasmas 19, 073303]用其他模型所得的结果基本一致; 电偶极、四极和八极极化率随Debye长度的变化趋势一致, 数值结果和Li和Kar [Li H W and Kar S, 2012 Phys. Plasmas 19, 073303] 的数量级一致.     

Calculations of induced moments in large molecules I. Polarizabilities and second hyperpolarizabilities in some alkanes

We report the results of coupled Hartree-Fock computations for the average polarizability, , and hyperpolarizability, , of CH₄, C₂H₆, C₃H₆ and C₃H₈. The Hamiltonian matrices are constructed from an extended CNDO model. Small as well as large basis sets were tested. Agreement with available experimental values is within 13% for and 31% for .     

Field and field-gradient polarizabilities of H2O

Using a charge-perturbation approach, all components of the polarizability tensors , , A, B, and C for H₂O have been evaluated at the SCF level and, with the exception of and B, at the MC SCF level of approximation. This is the first such comprehensive evaluation of the electrical properties of water.Member of the Ottawa-Carleton Chemistry Institute     

Direct evaluation of one-electron properties in coupled cluster methods

Summary An analysis of a method for approximate calculations of expectation values for one-electron operators from available coupled cluster amplitudes is presented and illustrated numerically for the polarizability of the Be atom. The one-particle density matrix resulting from the present approach is accurate through the fourth order in the electron correlation perturbation. It has been found that, in order to obtain quantitative agreement between the energy derivative results and the approximate expectation value formalism, the third orderT ₁ T ₂⁽⁰⁾ wave function term must be included into the calculation of the one-particle density matrix. The present method is also considered as a promising tool for calculations of higher-order atomic and molecular properties from high level correlated wave functions.     

DSC,density and refractive index studies on two nematogenic p-alkylphenyl-2-chloro-4-(p-alkylbenzoyloxy)-benzoates and their mixtures

The compounds p-pentylphenyl-2-chloro-4-(p-pentylbenzoyloxy)-benzoate [PCPB] and p-octylphenyl-2-chloro-4-(p-heptylbenzoyloxy)-benzoate [OCHB], and mixtures of different mole fractions of them, show a nematic phase with a supercooling effect. From DSC studies both ΔH and ΔS at T _NI are found to have minimum values for the equimolar mixture, which happens to be an eutectic mixture (Mix-II). However the density of this mixture is found to be less than that of the pure compounds. Refractive indices (n _o, n_e) are measured by thin prism method at different temperatures for pure components and the eutectic mixture. The birefringence values of the eutectic mixture are less than those of the individual components at higher temperature region, and are in-between at lower temperatures. The principal polarizibilities (α _o, α _e) of all the compounds have been calculated using both Vuks’ and Neugebauer's methods. These values have been compared with those calculated from additivity rules of bond polarizability. The average polarizability α increases with chain length. The orientational order parameter (P ₂) at different temperatures has been calculated using Haller's extrapolation procedure. (P ₂) values of OCHB are found to be greater than those of PCPB and Mix-II at higher temperatures, and are consistent with those determined from our X-ray studies. The temperature dependence of (P ₂) of all the compounds has been compared with Maier-Saupe theoretical values.