Lattice models of hydrogen-bonded solvents. II

We consider a lattice model of a binary mixture in which each molecule of one component can form zero, one, or two bonds to molecules of the same species on neighboring vertices of the square lattice. We allow the energy of molecules with two bonds to depend on the valence angle, thus generalizing the first paper in this series. If straight polymeric configurations are favored over all others, then a phase transition occurs for low enough temperature. On the other hand, if bent configurations are favored, there is no phase transition. Analogous results are obtained for the hexagonal lattice, where we distinguish energetically betweencis andtrans isomerism of four bonded molecules.Supported by the Danish Science Foundation under grant 511-3635.     

Hydrogen-bond dynamics near a micellar surface: origin of the universal slow relaxation at complex aqueous interfaces

The dynamics of hydrogen bonds among water molecules themselves and with the polar head groups (PHG) at a micellar surface have been investigated by long molecular dynamics simulations. The lifetime of the hydrogen bond between a PHG and a water molecule is found to be much longer than that between any two water molecules, and is likely to be a general feature of hydrophilic surfaces of organized assemblies. Analyses of individual water trajectories suggest that water molecules can remain bound to the micellar surface for more than 100 ps. The activation energy for such a transition from the bound to a free state for the water molecules is estimated to be about 3.5 kcal/mol.     

Temperature-responsive polymers in mixed solvents: competitive hydrogen bonds cause cononsolvency

If two good solvents become poor for a polymer when mixed, the solvent pair is called a cononsolvent pair. The sharp reentrant coil-to-globule-to-coil transition of a poly(N-isopropylacrylamide) chain observed in the mixed solvent of water and methanol is shown to be caused by the competitive hydrogen bonding by water and methanol molecules onto the polymer chain. On the basis of a new statistical-mechanical model for competitive hydrogen bonds, the mean square end-to-end distance is theoretically calculated and compared with experiment. The chain sharply collapses at the molar fraction xm approximately 0.2 of methanol, stays collapsed up to xm approximately 0.4, and finally recovers the swollen state at xm approximately 0.6. Such a reentrant coil-globule transition takes place because the total number of hydrogen bonds along the chain exhibits a similar square-well-type depression as a result of the competition.     

An NQR study of the polymorphism of triphenylchloromethane

This work is a study of the polymorphic transformations of triphenylchloromethane (TPCM) as well as the structure and dynamics of this molecular solid. Crystalline TPCM has been studied by a variety of techniques and many of its physical properties have been characterized. Previous crystallographic studies have reported the existence of two crystalline phases. Phase II, stable above 372 K, is trigonal with space group P3; and Z = 6. The compound associates pairwise (halogen-to-halogen and triphenylmethyl-to-triphenylmethyl) and linearly with all carbon-halogen bonds aligned with C3 and S6 axes of the lattice. Below 372 K, a triclinic modification (phase III) is found (P1;, Z = 10) where the molecules are also aligned pairwise with close Cl cdots, three dots, centered Cl interactions. However, the C-Cl bonds were no longer parallel. On the other hand, DTA studies have also reported a phase transition at 381 K (to phase I) that can been obtained from slow evaporation of pentane or ether solutions. Crystallographic information about these phases has not been obtained in the literature.Five NQR lines have been observed from liquid nitrogen temperature to 372 K in good agreement with phase III that has Z = 10. Above 372 K, three lines are observed which are related to phase II. Any effort to observe phase I through NQR failed; phase II remains until the sample is melted. Instead, if phase II is cooled down, a second-order phase transition to a new phase at 259 K is observed through NQR studies. The temperature dependence of experimental data in the phase transition region is well explained assuming the transitions occur when molecules in the crystal lattice change their direction uniformly with a change in temperature and the liberational modes, coupled in an anharmonic way with the uniform mode, change their frequencies in such a way that entropy compensates the unfavorable potential energy increase due to the uniform angular tilt.     

Influence of the metal nanofilm-semiconductor interface on surface properties of the nanofilm: The CO-Yb-Si(111) system

The influence of the “ytterbium nanofilm-single-crystal silicon substrate” interface on properties of the films has been investigated. It has been shown that, if the film thickness is less than 10 monolayers, the Friedel oscillations (standing waves of electron density) generated by the interface affect the work function of the films and the rate of adsorption of CO molecules on their surface. In turn, the CO molecules modify the electronic structure of ytterbium during adsorption on the surface of nanofilms by transforming ytterbium from the divalent to trivalent state. The completely filled layer of adsorbed CO molecules consists of two phases. The first phase is a two-dimensional gas whose molecules weakly interact with each other, but their lone electron pairs form a donor-acceptor bond with the Yb 5d level; as a result, this level is located below the Fermi level and the metal transforms into the trivalent state. After filling the two-dimensional phase, the second (island) phase, in which the CO molecule are bound by horizontal π-bonds, begins to grow. The formation of these bonds becomes possible due to the filling of 2π states in the molecules upon compaction of the adsorbed layer. The considered the adsorbed two-phase layer is responsible for the complete transition of ytterbium into the trivalent state.     

Separation and gelation in associated systems with thermoreversible chemical bonds

Possible types of separation curves for a binary solution of chemically interacting molecules in a neutral solvent have been analyzed within the statistical model. It has been shown that the variation of the model parameters characterizing the energy and entropy of chemical bonds makes it possible to describe most of the possible types of solubility curves within the unified formalism. It has been demonstrated that the sol-gel transition for the case where the reactivity of molecules depends on the number of bonds can occur as a first-order phase transition; in the opposite case, gelation is a purely geometrical percolation transition.     

Hydrophobic hydration at the level of primitive models. II: Large solutes and water restructuring

Details of structural changes that take place in water near an apolar solute have been studied by Monte Carlo simulations for hard sphere solutes of increasing size, including the limiting case of water at a hard structureless wall. Water has been modelled by two different types of extended primitive model, the four-site EPM4 model and five-site EPM5 model. Two different patterns of the orientational ordering of the water molecules around the solute as a function of its size have been found. For the EPM5 model, the structure of water and the orientation of its molecules near an apolar solute of finite diameter do not seem to be sensitive to the size of the solute, and only become more pronounced when the solute becomes a hard wall. On the other hand, the orientation ordering of the EPM4 molecules gradually changes with increasing size of the solute, and for solutes larger than approximately five times the size of the water molecule it is opposite to that near a small solute. A novel method to evaluate the excess chemical potential of large solutes has been implemented, and some thermodynamic quantities for water (distribution of hydrogen bonds and the excess chemical potential) have been computed as a function of the distance from the solute.     

Elastic Ising-like model for the nucleation and domain formation in spin crossover molecular solids

We investigate the nucleation, domain formation and propagation mechanisms observed in Spin Crossover materials, in the framework of an Ising-like model taking into account the elastic nature of the interactions. In Spin Crossover materials, the intermolecular coupling originates from a volume difference between the High Spin and the Low Spin molecular states and is simulated by anharmonic interaction potentials whose strengths are molecular-state-dependent. Using Monte Carlo methods, the phase diagram has been established. We show that the model contains both Ising short-range couplings and long-range elastic interactions. In particular, the results of long-range elastic models are reproduced. The introduction of lattice dynamics leads to the existence of spatial distributions of interaction energy and crystal field, corresponding to a local definition of physical properties. The nucleation process becomes highly dependent on the structural inhomogeneities induced by the spin transition. In this approach, connections strength between neighboring molecules are no more equivalent and have different ability to propagate domains. The presence of short-range Ising couplings gives rise to the occurrence of strong bonds forming a volume in which domains of the daughter phase can grow; in this case a macroscopic phase separation appears during the first order transition, even in a system with periodic boundary conditions. By contrast, in the case of a model with only long-range elastic interactions; strong bonds are uniformly spread in the lattice and a homogeneous phase transformation is observed, in good agreement with previous theoretical investigations.     

高分子凝胶体积相变中的氢键作用

我们把关联模型(association models)推广应用到高分子凝胶体系,研究高分子与溶剂分子间的氢键和溶剂分子与溶剂分子间的氢键在高分子凝胶体积相变中的作用.首先通过分析凝胶体积分数与温度的关系发现,由于两种氢键作用,随着温度变化高分子凝胶出现连续、不连续体积相变,结果表明在体积相变过程中两种氢键都起着重要作用.其次,对不同氢键分数条件下的旋节线的研究发现,对于高分子凝胶体积相变中出现的UCST和LCST(上临界共溶温度和下临界共溶温度)现象也是由于高分子与溶剂分子间氢键和溶剂分子与溶剂分子间氢键共同作用的结果.     

低强度周期量级脉冲驱动排列分子的非次序双电离

本文利用三维经典系综模型研究了低强度周期量级脉冲驱动排列分子的非次序双电离. 结果表明, 电子对的关联特性强烈地依赖于分子的排列方向和激光脉冲的载波包络相位; 垂直分子反关联电子对的比例总是高于平行分子反关联电子对的比例; 当载波包络相位从0到π 逐渐增加时, 反关联电子对的数目先增加再减少; 对于平行分子, 电子对的释放总是以正关联为主; 而垂直分子的主导关联模式则依赖于激光脉冲的载波包络相位, 当载波包络相位为0.3π-0.7π之间时, 电子对以反关联释放为主, 其他相位下以正关联为主. 本文利用分子势能曲线和电子返回能量很好地解释了电子关联特性对分子排列方向和载波包络相位的依赖关系.     

自旋为1的双层平方晶格阻挫模型的相变

采用双时格林函数方法研究了自旋为1的双层平方晶格阻挫模型的相变行为.详细探讨了层间耦合相互作用J_c和单离子各向异性参数D对奈尔态(AF1)和共线态(AF2)之间相转换的影响.结果显示:只要参数J_c和D不同时为零,奈尔态和共线态在J₂=J₁/2(这里J₁和J₂分别描述的是系统自旋间最近邻和次近邻交换作用)时的相变温度相等,两个态共存.在低于相变点的温度范围内,AF1-AF2态之间可以发生相转换,其相变类型为一阶相变.当J₂≠J₁/2时,尽管AF1-AF2态有不同相变温度,但它们也可以共存.如果AF1(AF2)态的相变温度大,在低温,AF1(AF2)态更稳定;在高温,AF2(AF1)态更稳定;在中间温度范围内,AF1-AF2态之间也可以发生一阶相转换.     

Molecular nanocluster fluorescence in microwave infrared-radiation fields

The paper considers a donor-acceptor nanocluster fluorescing in a microwave infrared radiation field. It is assumed that the nanocluster consists of two dipole-dipole interacting organic molecules. It is shown that the fluorescence process of the nanocluster occurs if the donor molecule contains a substructure of identical diatomic pairwise interacting bonds of dipoles (an IR antenna). This antenna is capable of accumulating vibrational energy as a sum of collective vibrational quanta (excimols). The acceptor molecule has no permanent dipole moment and cannot be excited by microwave IR radiation. This molecule is polarized in the dipole moment field of the donor IR antenna and can receive energy accumulated in the IR antenna of the donor molecule. If the acceptor molecule has an electronically excited state in the long-wavelength visible region of its absorption spectrum, then after receiving energy equal to the energy of this state from the donor antenna, the electronic excitation of the acceptor molecule and its fluorescence is possible. As an example, the fluorescence of a nanocluster is considered whose donor molecule has a C _n H_2n IR antenna. The acceptor molecule is aromatic and the external infrared frequency, 1.1 × 10¹⁴ s^?1, is equal to the frequency of the excimol in the donor infrared antenna.     

Crystalline phases of alkyl-thiol monolayers on liquid mercury

The structure of octadecanethiol monolyers on liquid Hg surfaces, measured with subangstrom resolution, evolves with increasing coverage from a laterally disordered phase of surface-parallel molecules to ordered rotator phases of surface-normal molecules. For the latter, an abrupt transition is found at 19 A(2)/molecule from a rectangular packing of molecules tilted by 27 degrees in the nearest-neighbor direction to a hexagonal unit cell of untilted molecules. The unit cell of the tilted phase is centered for the chains and noncentered for the headgroups. The thiol headgroups associate in pairs with a single Hg atom, and the bonds form long-range orientational order. The different order of thiols on Au(111) and on Hg highlights the subphase's role in determining the overlayer's structure.     

Biaxial nematic phase in the Maier-Saupe model for a mixture of discs and cylinders

We analyze the global phase diagram of a Maier-Saupe lattice model with the inclusion of shape-disordered degrees of freedom to mimic a mixture of oblate and prolate molecules (discs and cylinders). In the neighborhood of a Landau multicritical point, solutions of the statistical problem can be written as a Landau-de Gennes expansion for the free energy. If the shape-disordered degrees of freedom are quenched, we confirm the existence of a biaxial nematic structure. If orientational and disorder degrees of freedom are allowed to thermalize, this biaxial solution becomes thermodynamically unstable. Also, we use a two-temperature formalism to mimic the presence of two distinct relaxation times, and show that a slight departure from complete thermalization is enough to stabilize a biaxial nematic phase.     

石墨烯表面的特征水分子排布及其湿润透明特性的分子动力学模拟

石墨烯因其独特的分子构型、卓越的物理化学性能而受到广泛关注.本文首先利用分子动力学模拟比较了单层石墨烯、铜、二氧化硅三者表面的浸润性,除了接触角的比较,还分析了基底表面的水分子排布,得到石墨烯表面的特征水分子排布为:表面有两层密集的水分子层,其中靠近基底的密集水分子层中O—H键与垂直基底方向夹角集中在90°附近,并且基底表面的氢键几乎都垂直于基底.另一方面,本文研究了石墨烯浸润透明特性,发现在铜和二氧化硅上添加一层石墨烯,对铜的浸润性影响较小,对二氧化硅的浸润性影响很大,不仅使其上接触角显著增大,还使得基底表面的水分子排布呈现出类似单层石墨烯上的规律.本文使用分子动力学模拟方法从微观尺度验证了文献的实验结果,从基底表面水分子排布角度分析了石墨烯独特的浸润透明特性,为进一步开发石墨烯在微结构设计上的应用提供了理论指导.     

Investigation of the phase transition at the nematic liquid crystal-wall interface within nonextensivity

In this study, the nematic-isotropic phase transition is investigated for a sample in the shape of a slab of thickness d, using nonextensive formalism. The interaction potential is written as the sum of the direct interaction of a given nematic molecule with the substrate and of its incomplete interaction with the other nematic molecules due to the presence of the limiting surface. In this framework, we show the effects of the nonextensivity on the nematic-isotropic transition at the nematic-wall interface. The generalized model can shed light on the properties of nematic liquid crystal confined in small-scale structures.     

Nucleogenic iron studied by emission Mössbauer spectroscopy in Co-metal

Results obtained by means of the emission Mössbauer spectroscopy in metallic cobalt are reported. The Mössbauer line of the 14.4-keV energy connecting the first excited state of the stable ⁵⁷Fe nucleus with its ground state was used. Radioactive ⁵⁷Co was used as the precursor of the above nuclear state. It was dissolved in the natural metallic cobalt with the concentration of about 40 at. ppm including nucleogenic iron generated during decay of the cobalt precursor. Mössbauer spectra were collected in the temperature range between room temperature (RT) and 1075 K with the sample kept under vacuum. A transition from the low temperature hexagonal phase to the face centered cubic high temperature phase at about 690 K has no influence on the iron magnetic hyperfine field arising due to the ferromagnetic ordering of the host. On the other hand, the electron charge density on the iron nucleus has some relatively narrow maximum in the vicinity of the transition temperature. There is some discontinuity in the recoilless fraction as well indicating that the high temperature cubic phase provides somewhat stronger bonds for the isolated iron impurity. The anharmonic behavior of the lattice vibrations could be seen in the cubic phase well above the transition point. No measurable electric quadrupole interaction was found in the hexagonal phase. The evolution of the magnetic hyperfine field with the temperature is reasonably described by the spin wave formalism provided strong magnon-magnon scattering is allowed for. On the other hand, charge density on the iron nucleus follows thermal expansion except some singularity in the vicinity of the transition point.     

A unified model description of mobile and localized adsorption: II. Adsorption on crystalline surfaces — a gradual transition between mobile and localized adsorption

The model used in Part I is now extended to account for the periodic potential of the substrate. The influence of the energetical structure of the substrate on the state of motion of a single particle is allowed for at varying degree of coverage so that the gradual transition from localized to mobile adsorption with growing temperature may be described. The impact of the energetical characteristics of adsorbate and adsorbent on the critical parameters of the adsorption isotherms is investigated. These parameters are also considerably influenced when non-additivity of the lateral bonds is taken into account. On a perfectly smooth substrate, as well as in the case of potential wells of the substrate coinciding in size with the diameter of the adatoms, the model predicts the impossibility of a first order phase transition between “additive” and “nonadditive” phases. The last result could be related to the problem of 2D melting, provided the degree of disorder in both adsorbate phases is adequately expressed in terms of varying nonadditivity of the energy bonds.