String-like propagation of the 5-coordinated defect state in supercooled water: molecular origin of dynamic and thermodynamic anomalies

We find that at low temperature water, large amplitude (~60°) rotational jumps propagate like a string, with the length of propagation increasing with lowering temperature. The strings are formed by mobile 5-coordinated water molecules which move like a Glarum defect (J. Chem. Phys., 1960, 33, 1371), causing water molecules on the path to change from 4-coordinated to 5-coordinated and again back to 4-coordinated water, and in the process cause the tagged water molecule to jump, by following essentially the Laage-Hynes mechanism (Science, 2006, 311, 832-835). The effects on relaxation of the propagating defect causing large amplitude jumps are manifested most dramatically in the mean square displacement (MSD) and also in the rotational time correlation function of the O-H bond of the molecule that is visited by the defect (transient transition to the 5-coordinated state). The MSD and the decay of rotational time correlation function, both remain quenched in the absence of any visit by the defect, as postulated by Glarum long time ago. We establish a direct connection between these propagating events and the known thermodynamic and dynamic anomalies in supercooled water. These strings are found largely in the regions that surround the relatively rigid domains of 4-coordinated water molecules. The propagating strings give rise to a noticeable dynamical heterogeneity, quantified here by a sharp rise in the peak of the four-point density response function, χ(4)(t). This dynamics heterogeneity is also responsible for the breakdown of the Stokes-Einstein relation.     

A critical theoretical study on the two-photon absorption properties of some selective triaryl borane-1-naphthylphenyl amine based charge transfer molecules

In the present work, we have studied the two-photon absorption (TPA) properties of some selective molecules containing triarylborane and 1-naphthylphenylamine as the acceptor and donor moiety, respectively. The calculations are performed by using the state-of-the-art linear and quadratic response theory in the framework of the time dependent density functional theoretical method. The TPA parameters are calculated with CAMB3LYP functional and the cc-pVDZ basis set. The one-photon results indicate that both the electronic transitions (S(0)-S(1) and S(0)-S(2)) are associated with the charge transfer interaction between the donor and acceptor moieties along with the reorganization of the π-electron density. All these chromophores are found to have very strong two-photon active modes. In order to find out the origin of large TP transition probability of these molecules, we have performed two-state model (TSM) and sum-over-states (SOS) calculations. We have found that the TSM failed to reproduce the correct trend of the TP transition probability of the molecules obtained from the response theory, while SOS is quite successful in doing so. The whole study indicates that the transition moments between the excited states play a pivotal role in controlling the TP transition probabilities of these molecules. The role of solvent in the TP transition probability of these molecules has meticulously been scrutinized within the polarized continuum model (PCM). Further more, we have benchmarked our theoretical findings by calculating the TPA cross-section of a boron and nitrogen containing a charge transfer molecule for which the experimental result is available and we found that our theoretical result is in good agreement with the experimental one which definitely demonstrates the potential of all these light-emitting diode molecules as TP active materials too.     

Simulation of Benzenesulfonyl Chloride Hydrolysis. Influence of the Size and Structural Ordering of Aqueous Clusters on Thermodynamic and Activation Parameters of the Process

The potential energy surfaces for hydrolysis of benzenesulfonyl chloride in clusters incorporating one to three additional water molecules (along with the molecule acting as nucleophile) were calculated by the PM3 method in the supermolecular approximation. As in the gas phase, hydrolysis of benzenesulfonyl chloride in clusters is a two-step exothermic process occurring via relatively unstable five-coordinate inter- mediate. The structural and thermodynamic parameters of the intermediate and transition states of the reaction, and also the thermodynamic functions of the process were calculated for seven clusters of different structures.     

Statistical mechanical theory for discotic liquid crystals Discotic nematic-isotropic transition properties

A statistical mechanical theory is applied to study the equilibrium properties of discotic nematic liquid crystals. We report the calculation of thermodynamic properties for a model system composed of molecules interacting through angle-dependent pair potentials which can be broken up into rapidly varying short-ranged repulsions and weak long-range attractions. The repulsive interaction is represented by a repulsion between hard oblate ellipsoids of revolution and is a short-range, rapidly-varying, potential. The influence of attractive potentials, represented by dispersion and quadrupole interactions on a variety of thermodynamic properties is analysed. It is found that the thermodynamic properties for the discotic nematic-isotropic transition are highly sensitive to the form of effective one-body orientational perturbation potential. The discontinuity in the transition properties is more pronounced in the case of quadrupole interaction than for anisotropic dispersion interaction. A remarkable symmetry in the transition properties between prolate ellipsoids (ordinary nematic) and oblate ellipsoids (discotic nematic) is observed.     

Apparent First‐Order Liquid–Liquid Transition with Pre‐transition Density Anomaly,in Water‐Rich Ideal Solutions

The striking increases in response functions observed during supercooling of pure water have been the source of much interest and controversy. Imminent divergences of compressibility etc. unfortunately cannot be confirmed due to pre‐emption by ice crystallization. Crystallization can be repressed by addition of second components, but these usually destroy the anomalies of interest. Here we study systems in which protic ionic liquid second components dissolve ideally in water, and ice formation is avoided without destroying the anomalies. We observe a major heat capacity spike during cooling, which is reversed during heating, and is apparently of first order. It occurs just before the glassy state is reached and is preceded by water‐like density anomalies. We propose that it is the much‐discussed liquid–liquid transition previously hidden by crystallization. Fast cooling should allow the important fluctuations/structures to be preserved in the glassy state for leisurely investigation.     

Apparent First‐Order Liquid–Liquid Transition with Pre‐transition Density Anomaly,in Water‐Rich Ideal Solutions

The striking increases in response functions observed during supercooling of pure water have been the source of much interest and controversy. Imminent divergences of compressibility etc. unfortunately cannot be confirmed due to pre‐emption by ice crystallization. Crystallization can be repressed by addition of second components, but these usually destroy the anomalies of interest. Here we study systems in which protic ionic liquid second components dissolve ideally in water, and ice formation is avoided without destroying the anomalies. We observe a major heat capacity spike during cooling, which is reversed during heating, and is apparently of first order. It occurs just before the glassy state is reached and is preceded by water‐like density anomalies. We propose that it is the much‐discussed liquid–liquid transition previously hidden by crystallization. Fast cooling should allow the important fluctuations/structures to be preserved in the glassy state for leisurely investigation.     

PuC2 气态分子的结构与热力学稳定性研究

在相对论有效原子实势近似下,用密度泛函B3LYP方法,求得PuC2气态分子的结构与不同温度下的热力学函数.根据热力学原理,计算得到PuC2气态分子在不同温度下的标准生成自由能变均为较大正值,据此说明, PuC2气态分子不具有热力学稳定性.     

Thermodynamic properties of chiral liquid crystalline material (S)-4-(2-methylbutyl)-4′-cyanobiphenyl (5*CB)

As a part of a project of clarifying the physical properties and dynamics of cyanobiphenyls with chiral molecules, thermodynamic properties of (S)-4-(2-methylbutyl)-4′-cyanobiphenyl (5*CB) were investigated by adiabatic calorimetry between T = (5 and 350) K. The complicated phase behaviour was solved and the thermodynamic functions were determined. A new glass transition was identified in the phase II (metastable crystal) at T = 105 K. No inversion of the stability between two crystalline phases was found, being contrary to the expectations from the previous neutron scattering studies.     

Origin of the dynamic transition upon pressurization of crystalline proteins

We study the role of hydration water in the dynamic transition of low-hydrated proteins upon pressurization found recently (Meinhold, L.; Smith, J. C. Phys. Rev. E 2005, 72, 061908). Clustering and percolation of water in the hydration shells of protein molecules in crystalline Staphylococcal nuclease are analyzed at various pressures. The number of water molecules in the hydration shell increases and the hydrogen-bonded network of hydration water spans with increasing pressure. The dynamic transition of protein occurs when the spanning water network exists with the probability of about 50% and hydration water shows large density fluctuations. Formation of a spanning water network upon pressurization promotes protein dynamics as in the case of the dynamic transition with increasing hydration. Properties of hydration water in various thermodynamic states and their influence on biological function are discussed.     

Two-dimensional facets in Langmuir monolayers of 1-O-hexadecyl-rac-glycerol at the air-water interface

We study the surface phase behavior in Langmuir monolayers of 1-O-hexadecyl-rac-glycerol (C16G) by film balance and Brewster angle microscopy over a wide range of temperatures. A cusp point followed by a pronounced plateau region in the pressure-area (pi-A) isotherm indicates a first-order phase transition between a lower density liquid expanded (LE) phase and a higher density liquid condensed (LC) phase at the air-water interface. A wide variety of condensed domains are found to form just after the appearance of the cusp point. The observed surface morphology was compared with that of ethylene glycol mono-n-hexadecyl ether (C16E1) that bears an ethylene oxide (EO) unit in the head-group. As usually observed, the domains of C16E1 are found to be circular at lower temperatures and fractal at higher temperatures. Contrary to this usual behavior, the domains of C16G are found to be strip-like structures at lower temperatures, which attain increasingly compact shape as the temperature increases and finally attain faceted structures at > or = 25 degrees C. It is concluded that a higher degree of dehydration around the head-group region of C16G appreciably reduces the hydration-induced repulsive interactions between the head-groups and imparts to the molecules an increase in hydrophobicity, thereby a closer molecular packing. As a result, the molecules form increasingly compact domains as the temperature increases. Since the head-group of C16E1 is much smaller than that of C16G, dehydration effect cannot appreciably increase its hydrophobic character. Rather, increases in subphase temperature result in a decrease in the line tension of the interface giving fractal structures at higher temperatures. In addition, the changes in enthalpy (deltaH) and entropy (deltaS) values were also calculated to understand the thermodynamic nature of condensation of the molecules in the LE-LC transition region.     

Thermodynamic properties of 1,3-dimethylsilatrane and 1-(2-cyanoethyl)silatrane

The heat capacities of 1,3-dimethylsilatrane and 1-(2-cyanoethyl)silatrane were measured, and their thermodynamic functions were calculated. In the intervals 12–205 and 215–315 K, the heat capacity of 1,3-dimethylsilatrane smoothly varies with temperature. A reproducible thermal effect is observed at ～315 K, and a G-type transition, in the range 205–215 K. 1-(2-Cyanoethyl)silatrane shows no anomalies in the examined temperature range. Above 260 K, the rate of the growth of the heat capacity with temperature increases.     

Ab initio investigation of ammonia-borane complexes for hydrogen storage

The structural, electronic, and thermodynamic properties of ammonia-borane complexes with varying amounts of hydrogen have been characterized by first principles calculations within density functional theory. The calculated structural parameters and thermodynamic functions (free energy, enthalpy and entropy) were found to be in good agreement with experimental and quantum chemistry data for the crystals, dimers, and molecules. The authors find that zero-point energies change several H2 release reactions from endothermic to exothermic. Both the ammonia-borane polymeric and borazine-cyclotriborazane cycles show a strong exothermic decomposition character (approximately -10 kcal/mol), implying that rehydrogenation may be difficult to moderate H2 pressures. Hydrogen bonding in these systems has been characterized and they find the N-H bond to be more covalent than the more ionic B-H bond.     

Structural and vibrational properties of vanadium (III) oxofluoride and oxochloride—a theoretical study

The potential energy surfaces of FVO and ClVO are studied using the density functional theory. It is found that the potential energy surface of both molecules is dominated by triplet states. Several singlet states are found close in energy, though. A good agreement is found between experimental and calculated vibrational frequencies except for the V–F stretching mode, which is predicted to be too low by the present results. The frequencies corresponding to the O–V–X bending mode are provided as a guide for future experimental studies. An estimation of the force constants, mean amplitudes of vibration, and thermodynamic functions is performed, too, in order to get a deeper insight into the bond properties of the title molecules.     

On the conformational effects of intermolecular interactions in nematics

A perturbation expansion of the pair correlation function is used to derive the molecular field self-consistency equations for non-rigid molecules. The order parameters and the thermodynamic functions are expressed directly in terms of the segmental interaction coupling constants. The values of these constants for the 4-n-alkyl-4'-cyanobiphenyis (NCB) are determined by analysing the orientational order parameters observed by N.M.R. in the nematic phase; they are in reasonable agreement with values obtained from calculations of the nematic-isotropic transition temperatures. It is found that contributions of the isotropic intermolecular interactions to the conformational energy of the alkyl chain are comparable in magnitude to the direct intramolecular contributions.     

Structural anomalies for a three dimensional isotropic core-softened potential

Using molecular dynamics simulations we investigate the structure of a system of particles interacting through a continuous core-softened interparticle potential. We found for the translational order parameter t a local maximum at a density rho(t-max) and a local minimum at rho(t-min)>rho(t-max). Between rho(t-max) and rho(t-min), the t parameter anomalously decreases upon increasing pressure. For the orientational order parameter Q(6) a maximum was observed at a density rho(t-max)相似文献   

Structural phase transitions in pentacosane C25H52

The pentacosane undergoes a series of structural phase transitions in addition to the melting transition according to an x-ray scattering study. A phenomenological theory is developed to describe the structural phase transitions between different phases observed in pentacosane. We present a detailed analysis of the different phases and analyze the temperature anomalies of the elastic constants and heat capacity. The thermodynamic anomalies on the different phase transitions are described by the coupling between the order parameters and the elastic strains. The theoretical predictions are found to be in good qualitative agreement with experimental results.     

Multi-structural thermodynamics of C-H bond dissociation in hexane and isohexane yielding seven isomeric hexyl radicals

The C-H bond dissociation processes of n-hexane and isohexane involve 23 and 13 conformational structures, respectively in the parent molecules and 14-45 conformational structures in each of the seven isomeric products that we studied. Here we use the recently developed multi-structural (MS) thermodynamics method and CCSD(T)-F12a/jul-cc-pVTZ//M06-2X/6-311+G(2df,2p) potential energy surfaces to calculate the enthalpy, entropy, and heat capacity of n-hexane, isohexane, and seven of the possible radical products of dissociation of C-H bonds. We compare our calculations with the limited experimental data and with values obtained by group additivity fits used to extend the experimental data. This work shows that using the MS method involving a full set of structural isomers with density functional geometries, scaled density functional frequencies, and coupled cluster single-point energies can predict thermodynamic functions of complex molecules and bond dissociation reactions with chemical accuracy. The method should be useful to obtain thermodynamic data for complex molecules for which such data has not been measured and to obtain thermodynamic data at temperatures outside the temperature range where measurements are available.     

Influence of temperature and alkyl chain length on phase behavior in Langmuir monolayers of some oxyethylenated nonionic surfactants

We study the surface phase behavior in Langmuir monolayers of a series of nonionic surfactants of the general formula CnE1 with n=14, 16, and 18 by film balance and Brewster angle microscopy (BAM) over a wide range of temperatures. A cusp point followed by a pronounced plateau region in the pressure-area (pi-A) isotherms indicates a first-order phase transition in the coexisting state between a lower density liquid expanded (LE) phase and a higher density liquid condensed (LC) phase at the air-water interface. The formation of bright two-dimensional (2D) LC domains in a dark background visualized by BAM further confirms this observation. In addition to the cusp point at the onset of the LE-LC coexistence state, another cusp point followed by a small plateau is observed for the C14E1 and C18E1 monolayers, indicating a second phase transition between two condensed phases of different compressibility and tilt orientation of the molecules. This unusual two-step phase transition is explained by the Ostwald step rule. The C16E1 and C18E1 monolayers show a kink in their respective isotherms, after which the surface pressure increases steeply with only a little decrease in the molecular area, suggesting that the molecules undergo a transition from a tilted to an almost vertical orientation with respect to the water surface. The thermodynamic parameters for the condensation of the molecules in the LE-LC coexistence state were calculated by employing the 2D Clapeyron equation. The temperature coefficient of the critical surface pressure dpi(c)/dT values shows a decreasing trend from C14E1 to C18E1, suggesting that the condensation process becomes less and less prone to thermal perturbation as the chain length increases. For all the amphiphiles, the DeltaH values are found to be negative, suggesting an exothermic nature of condensation. The negative DeltaS values obtained from the relation DeltaH/T probably come from the restriction on the rotational and translational motion of the molecules constrained in a confined area in the LE-LC transition region.     

环五甲撑五硝胺(CRX)结构和性质的DFT预示

用密度泛函理论(DFT)B3LYP方法,在6-31G*基组水平下,全优化计算了环五甲撑五硝胺(CRX)的分子几何和优化构型下的电子结构.环C-N键长为0.144～0.148 nm, N-NO2键长为0.139～0.142 nm; CRX的最高占有MO(HOMO)能级和最低未占MO(LUMO)能级之间的差值ΔEg(5.2054 eV)较大,预示CRX较稳定.基于简谐振动分析求得IR谱频率和强度.运用统计热力学方法,求得在200～1200 K的热力学性质C0p,m、 S0m和H0m.还运用Kamlet公式预示了它的爆速和爆压分别为9169 m/s和37.88 GPa.