Relationship between the internal pressure and cohesive energy density of liquids

The concepts of internal pressure and cohesive energy density of liquids are considered. Conditions of equality between the internal pressure and the cohesive energy density are revealed.     

Volumetric coefficients,internal pressure,and cohesion energy density of <Emphasis Type="Italic">n</Emphasis>-alcohols

Changes in the thermal expansion coefficient and isothermal compressibility in homological series of n-alcohols at 298 K are discussed. It is shown that only methanol exhibits abnormal behavior. Volumetric coefficients of hypothetical solvents such as pseudo-water and pseudo-methanol are determined. Internal pressure values of liquids are calculated. The internal pressure of pseudo-water exceeds that of water, whereas the situation is opposite for the cohesion energy density.     

Relationship between the internal pressure and cohesive energy density of a liquid nonelectrolyte. Consequences of application of Dack’s concept

Dack’s concept that correlates internal pressure with cohesive energy density of a liquid system is shown to be applicable to identification of energy and structural changes in series of alkanols: MeOH, EtOH, n-PrOH, (i-PrOH), and n-BuOH, (t-BuOH). The side chain of methyl groups that appears in the molecule loosens the structural packing of the alkanol, creating additional steric hindrances for stable hydrogen bonds in alcohol media.     

To the Understanding of the Structural Sensitivity of the Temperature Coefficient of Internal Pressure

The previously found empirical relationships between the temperature coefficient of internal pressure, on the one hand, and the structure and its evolution in liquids due to variations of temperature and concentration, on the other, are interpreted in terms of the peculiarities of intermolecular interactions. Analysis has revealed that the curves of the temperature dependences of internal pressure P _i(T) of associated liquids are directed upward by their concavity; they have a minimum and asymptotically tend toward P _i = 0 at T→∞. The curves P _i(T) of weakly associated liquids are directed downward by their concavity and have no extrema, but asymptotically tend to zero at T→∞.Original Russian Text Copyright © 2004 by V. N. Kartsev__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 877–882, September–October, 2004.     

Relationships between the internal pressure,the cohesive energy,and the surface tension of liquids

The relationship between the internal pressure P_int on the one hand and the cohesive energy density ced on the other and the ratio of the surface tension to the cube root of the molar volume σ/V^1/3 (also called the Gordon parameter) was examined for a large number of liquids. These consisted of four classes: molecular liquids, liquid metals, room temperature ionic liquids (RTILs), and molten salts. Linear dependences, rather than proportionalities suggested by theory, were obtained in all cases, their slopes being independent of the type of the liquid (the exceptions being noted), but differ for P_int and ced.     

Internal pressure and cohesive energy density for binary non-electrolyte mixtures

Internal pressures and cohesive energy densities of binary liquid mixtures of n-pentane+dichloromethane, n-pentane+methylacetate, 2-propanol+methylacetate and n-bytylamine+1,4-dioxane at 25°C have been evaluated from molar volumes surface tensions and enthalpies. The data obtained provide information about interactions in the binary liquid mixtures which can be correlated with results from other thermodynamic properties.Presented at the VI Congreso Argentino de Fisicoquímica, Santiago del Estero, Argentina, 1989.     

Structral and thermodynamic characteristics and intermolecular interactions in aqueous solutions of diols

The structural and thermodynamic characteristics of aqueous solutions of ethanediol, 1,2-and 1,3-propanediols, and 1,2-and 1,4-butanediols were calculated over the whole range of the compositions of the mixtures. The specific and nonspecific components of the total energy of intermolecular interactions were determined. The boundaries of the concentration regions with different structural organizations of solutions were established, and the parameters of preferable solvation of the solution components were evaluated.     

Structural and thermodynamic parameters and intermolecular interactions in aqueous formic acid amides

The structural and thermodynamic characteristics of aqueous solutions of formamide, N-methylformamide, N,N-dimethylformamide, and N,N-diethylformamide were calculated. The specific and nonspecific components of the total energy of intermolecular interactions were determined. The limits of the concentration regions with differently arranged structures of solutions were established, and the preferable solvation parameters of the solution components were evaluated.     

Relation between characteristic adsorption energy and internal pressure in the theory of volume filling of micropores

An equation for the internal pressure acting on an adsorbate in micropores was obtained on the basis of the assumption that the chemical potential of an adsorbate in micropores is equal to that in an equilibrium gas phase and using the Dubinin-Radushkevich equation. The empirical relation between the characteristic adsorption energy and the half width of pores was expressed in terms of internal pressure and diameter of adsorbate molecules. The two-dimensional pressure was calculated for micropores with plane-parallel walls, where the width of a micropore coincides with the diameter of an adsorbate molecule. The results obtained were compared with the two-dimensional pressure of a monolayer on a free planar surface for an adsorbate and adsorbent of the same nature.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1928–1930, October, 1995.     

Structural thermodynamic parameters and intermolecular interactions in aqueous solutions of secondary amides

Structural thermodynamic parameters are calculated for aqueous solutions of secondary amides of carboxylic acids. Specific and nonspecific contributions to the total energy of intermolecular interactions are determined and the boundaries of concentration regions for a various structural organization of solutions are found.     

Application of reference‐modified density functional theory: Temperature and pressure dependences of solvation free energy

Recently, we proposed a reference‐modified density functional theory (RMDFT) to calculate solvation free energy (SFE), in which a hard‐sphere fluid was introduced as the reference system instead of an ideal molecular gas. Through the RMDFT, using an optimal diameter for the hard‐sphere reference system, the values of the SFE calculated at room temperature and normal pressure were in good agreement with those for more than 500 small organic molecules in water as determined by experiments. In this study, we present an application of the RMDFT for calculating the temperature and pressure dependences of the SFE for solute molecules in water. We demonstrate that the RMDFT has high predictive ability for the temperature and pressure dependences of the SFE for small solute molecules in water when the optimal reference hard‐sphere diameter determined for each thermodynamic condition is used. We also apply the RMDFT to investigate the temperature and pressure dependences of the thermodynamic stability of an artificial small protein, chignolin, and discuss the mechanism of high‐temperature and high‐pressure unfolding of the protein. © 2017 Wiley Periodicals, Inc.     

Quantum chemical studies on the structure and detonation properties of the fused polynitrodiazoles: New high energy density molecules

In this study, we explore the possibility that fused polynitrodiazoles act as high energy density materials. Density functional theory calculations at the B3LYP/aug‐cc‐pVDZ level were performed to predict the structure, energy of explosion (≈1.68 kcal g^?1), density (≈1.98 g cm^?3), detonation velocity (≈9.50 km s^?1), and detonation pressure (≈41.50 GPa) of model molecules. The predicted properties have been found to be promising compared with 3,4,5‐trinitro‐1H‐pyrazole, 1,3,5‐trinitro‐1,3,5‐triazinane, and octahydro‐1,3,5,7‐tetranitro‐l,3,5,7‐tetraazocane. The nature of azoles of the molecule presumably determines the geometry, stability, sensitivity, density, and detonation performance. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

On Internal Pressure, Its Temperature Dependence, and the Structure of Liquid-Phase Systems

The notions of internal pressure and its temperature coefficient are critically analyzed. The temperature coefficient of internal pressure is correlated with the peculiarities of supramolecular organization of liquid-phase systems. This relationship is characterized.     

Theoretical study of atoms by the electronic kinetic energy density and stress tensor density

The electronic structure of atoms in the first, second, and third periods were analyzed using the electronic kinetic energy density and stress tensor density, which are local quantities motivated by quantum field theoretic consideration, specifically the rigged quantum electrodynamics. The zero surfaces of the electronic kinetic energy density, which are called as the electronic interfaces, of the atoms were computed. It was found that their sizes exhibited clear periodicity and were comparable to the conventional atomic and ionic radii. The electronic stress tensor density and its divergence, tension density, of the atoms, were also computed and how their electronic structures were characterized by them was discussed. © 2016 Wiley Periodicals, Inc.     

Energy transfer dynamics and kinetics of elementary processes (promoted) by gas‐phase CO2‐N2 collisions: Selectivity control by the anisotropy of the interaction

In this work, we exploit a new formulation of the potential energy and of the related computational procedures, which embodies the coupling between the intra and intermolecular components, to characterize possible propensities of the collision dynamics in energy transfer processes of interest for simulation and control of phenomena occurring in a variety of equilibrium and nonequilibrium environments. The investigation reported in the paper focuses on the prototype CO₂–N₂ system, whose intramolecular component of the interaction is modeled in terms of a many body expansion while the intermolecular component is modeled in terms of a recently developed bonds‐as‐interacting‐molecular‐centers' approach. The main advantage of this formulation of the potential energy surface is that of being (a) truly full dimensional (i.e., all the variations of the coordinates associated with the molecular vibrations and rotations on the geometrical and electronic structure of the monomers, are explicitly taken into account without freezing any bonds or angles), (b) more flexible than other usual formulations of the interaction and (c) well suited for fitting procedures better adhering to accurate ab initio data and sensitive to experimental arrangement dependent information. Specific attention has been given to the fact that a variation of vibrational and rotational energy has a higher (both qualitative and quantitative) impact on the energy transfer when a more accurate formulation of the intermolecular interaction (with respect to that obtained when using rigid monomers) is adopted. This makes the potential energy surface better suited for the kinetic modeling of gaseous mixtures in plasma, combustion and atmospheric chemistry computational applications. © 2016 Wiley Periodicals, Inc.     

Similarities and Differences between Crystal and Enzyme Environmental Effects on the Electron Density of Drug Molecules

The crystal interaction density is generally assumed to be a suitable measure of the polarization of a low-molecular weight ligand inside an enzyme, but this approximation has seldomly been tested and has never been quantified before. In this study, we compare the crystal interaction density and the interaction electrostatic potential for a model compound of loxistatin acid (E64c) with those inside cathepsin B, in solution, and in vacuum. We apply QM/MM calculations and experimental quantum crystallography to show that the crystal interaction density is indeed very similar to the enzyme interaction density. Less than 0.1 e are shifted between these two environments in total. However, this difference has non-negligible consequences for derived properties.     

An absolute droplet pressure interfacial tensiometer and its application to bituminous systems of vanishing density contrast

Experimental problems preclude or limit measurements of interfacial tension in bitumen or extra-heavy crude oil-containing systems when there exists a vanishing density difference between the phases. We describe a novel droplet pressure method that allows such measurements to be made. This method is based on a liquid/liquid adaptation of the capillary displacement differential maximum bubble pressure surface tension method of Schramm and Green [29]. In this method, interfacial tension is calculated from the difference between maximum droplet pressures reached at capillaries of differing internal radii, immersed to slightly different depths. The elimination of the influence of liquid densities allows the measurement of interfacial tensions without independently determining the liquid densities, and in particular, permits measurements in systems for which the density difference is vanishingly small. The absolute measuring technique is illustrated for several systems of pure and practical liquids. Received: 8 March 2000/Accepted: 30 May 2000     

Influence of the size of fixed-rigidity spheres on the structural and energy characteristics of hydrophobic hydration

Monte Carlo simulations of molecular configurations of aqueous solutions of spherical particles with a special potential of solute—water interaction were carried out. The influence of the particle size on the properties of hydration shells was investigated. Two regimes of hydrophobic hydration with a crossover point at 0.4 nm were found. Hydration of smaller particles causes insignificant changes in the properties of water. Particles larger than 0.4 nm break the liquid water structure. Breaking effects are more pronounced in the first hydration shell of particles. Dewetting of hard sphere surfaces predicted by the LCW phenomenological theory has peculiarities in the case of hydration of fixed-rigidity spheres. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1777–1786, September, 2008.     

Self‐energy fields solutions to the generalized reduced Liouville equation in the perturbative approach

A direct approach for the generalized reduced Liouville equation of motion decoupling problem associated with open quantum systems within the superoperator formalism is presented. The procedure is based on inversion of the perturbation series for the energy representation of the density operator so as to obtain one for the proper self‐energy fields that emerge as a consequence of the analytic character of the associated spectral representation. Thus, the perturbation series that arises from the iteration of the energy‐dependent matrix elements hierarchy involved in the statistical operator allows, upon further expansion of the inverse of such series, to get formally exact expressions for the corrections to all orders of the self‐energy fields. The lower order corrections of these fields are discussed in terms of resonant and nonresonant contributions. The present approach provides matrix equations that show the close relation between the environment effects represented by the self‐energy fields and the relaxation kernel that drives the system–reservoir interaction. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 280–290, 2000     

Electron energy structure and X-ray spectra of wide-band GaN, AlN, and AlN-GaN semiconductors

The electronic energy structure of GaN, AlN, and AlGaN crystals with the wurzite structure is calculated by the local coherent potential method using the cluster version of the MT-approximation within the framework of the multiple scattering theory. The calculated densities of electron states are compared with XPS spectra of gallium and aluminum, AlL _{II, III} XES, and also with K-spectra of gallium and AlL _{II, III} XAFS absorption. The comparison of the electronic structure of Al_xGa_1?x N crystals and binary GaN and AlN and the interpretation of their features are performed. The concentration dependence of the width of the upper subband of the valence band and the band gap in Al_xGa_1?x N (x = 0, 0.25, 0.5, 0.75, 1) crystals on the content of aluminum is studied and its non-linear character shown.