Can octupolar molecules be poled by an external electric field?

Octupolar molecules are generally believed to be of potential use in developing nonlinear optical materials owing to the fact that they do not easily form molecular aggregates. This is often put against the conjectured drawback that electric fields have no poling, or ordering, effect for this class of molecules because of the lack of a permanent ground state dipole moment. In this paper, we analyze this notion in some detail and present results from molecular dynamics computer simulations of an ensemble of a prototypical octupolar molecule, the 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) molecule, dissolved in chloroform. It is found that TATB molecules indeed show rather significant dipole moments in solutions because of the dual action of the thermal motions of the atoms and the strong intermolecular interactions. Applied electric fields accordingly show significant effects on the orientations of the molecular dipole moments. We also find that TATB molecules can aggregate because of the strong hydrogen-bonding interactions between the molecules, though they lack a static permanent dipole moment. Thus, the simulation results for TATB molecules in solution present us with a totally different notion about the collective properties of octupolar molecules. Taking account of quantum chemistry results, we found that the collective molecular nonlinear optical (NLO) properties are enhanced after the onset of the electric field, showing significant anisotropic characteristics.     

Understanding the solubility of triamino-trinitrobenzene in hydrous tetramethylammonium fluoride: a first principles molecular dynamics simulation study

With the aim to understand the relatively high solubility of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), an important energetic material with a high degree of inter- and intra-molecular hydrogen bonding, in fluoride anion containing ionic liquids (ILs), first principles molecular dynamics simulations in the isobaric-isothermal ensemble were carried out for a system using hydrous tetramethylammonium fluoride as the prototypical solvent. Simulations initiated from both molecular TATB and its Meisenheimer complex (i.e., a σ-complex of the fluoride and the electrophilic ring of TATB) yield a Zundel-type complex where a proton is shared between an amino group and an F(-) ion, whereas the Meisenheimer complex is found to be only transiently stable. An analysis of the electronic structure probing the Wannier function centers supports the finding of a proton-sharing complex with a three-center four-electron like bond. The Zundel-type complex also yields an electronic absorption spectrum consistent with the experimentally observed color change. This study provides evidence that the remarkable solubility of otherwise hard-to-dissolve molecular crystals in ILs can be aided by chemical modification of the solute.     

Pi-stacked interactions in explosive crystals: buffers against external mechanical stimuli

The pi-stacked interactions in some explosive crystal packing are discussed. Taking a typical pi-stacked explosive 2,4,6-trinitrobenzene-1,3,5-triamine (TATB) as a sample and using molecular simulations, we investigated the nature of the pi-stacked interactions versus the external mechanical stimuli causing possible slide and compression of explosives. As a result, between the neighbor layers in the TATB unit cell, the electrostatic attraction decreases with a little decrease of vdW attraction when its top layer slides, whereas the vdW attraction increases with a decrease of electrostatic attraction when TATB crystal is compressed along its c axis. Meanwhile, we studied the correlation between the pi-stacked structures and the impact sensitivities of explosives by means of three representatives including TATB with typical planar pi-stacked structures, 2,2-dinitroethylene-1,1-diamine (Fox-7) with wavelike pi-stacked structures, and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) without pi-stacked structure. The results showed that pi-stacked structures, particularly planar layers, can effectively buffer against external mechanical stimuli. That is, pi-stacked structures can partly convert the mechanical energy acting on them into their intermolecular interaction energy, to avoid the increase of the molecular vibration resulting in the explosive decomposition, the formation of hot spots, and the final detonation. This is another reason for the low mechanical sensitivity of pi-stacked explosives besides their stable conjugated molecular structures.     

VDF-CTFE共聚物在TATB表面吸附链构象的分子动力学模拟

采用COMPASS力场和NVT正则系综的动力学计算模拟了偏氟乙烯(PVDF)与三氟氯乙烯(PCTFE)及其共聚物在1,3,5-三氨基-2,4,6-三硝基苯(TATB)表面吸附能和吸附链的构象. 结果表明, 氟聚合物链与TATB表面距离小于0.8 nm时, 产生吸附放热效应. 在TATB表面, PVDF有强吸附作用, 而PCTFE的吸附能力差. 对VDF与CTFE单体摩尔比为1∶1, 1∶2, 1∶3和1∶4的共聚物吸附模拟结果表明, 共聚物的组成和链的序列结构对其在TATB表面的吸附行为和吸附链构象影响很大. 单体摩尔比为1∶2的交替共聚物链的吸附效果最佳. 随着共聚物链段中PCTFE链节的增加, 聚合物链的刚性增大, 在TATB表面吸附能力逐渐下降、吸附能亦降低, 尾型(tail)或环型(loop)构象数逐渐增多.     

Two-photon absorption of hydrogen-bonded octupolar molecule clusters

Charge-transfer octupolar molecules can form clusters in solution through intermolecular hydrogen bonds. In the present work we explore the role of such clustering on two-photon absorption (TPA) spectra assuming 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) as a model system. Using density functional quadratic response theory we examine different cluster structures of TATB dimers, trimers, and tetramers taken from snapshots of molecular dynamics simulations. In comparison with the TPA spectrum of a monomer, significant red shifts of charge-transfer states are predicted for all chosen clusters, which mainly is the result of the distortion of the structures induced by the aggregation. The TPA spectra for dimers and trimers show strong conformation dependence, whereas they turn out to be more stable for tetramers. Enhancements of TPA absorption have also been found for clusters containing less distorted molecules connected by hydrogen bonds.     

A comparative molecular simulation study of the glass former ortho-terphenyl in bulk and freestanding films

We performed molecular dynamics simulations of the low-molecular weight organic glass former ortho-terphenyl in bulk and freestanding films. The main motivation is to provide molecular insight into the confinement effect without explicit interfaces. Based on earlier models of ortho-terphenyl we developed an atomistic model for bulk simulations. The model reproduces literature data both from simulations and experiments starting from specific volume and diffusivity to mean square displacement and radial distribution functions. After characterizing the bulk model we form freestanding films by the elongation and expansion method. These films give us the opportunity to study the dynamical heterogeneity near the glass transition through in-plane mobility and reorientation dynamics. We finally compare the model in bulk and under confinement. We found qualitatively a lower glass transition temperature for the freestanding film compared to the bulk.     

Mechanism of densification in silica glass under pressure as revealed by a bottom-up pairwise effective interaction model

A new short-range pairwise numerical potential for silica is presented. The potential is derived from a single ab initio molecular dynamics (AIMD) simulation of molten silica using the force-matching method with the forces being represented numerically by piecewise functions (splines). The AIMD simulation is performed using the Born-Oppenheimer method with the generalized gradient approximation (BLYP) for the XC energy functional. The new effective potential includes a soft-repulsive shoulder to describe the interactions of oxygen ions at short separations. The new potential, despite being short-ranged and derived from single-phase data, exhibits a good transferability to silica crystalline polymorphs and amorphous silica. The importance of the O-O soft-repulsive shoulder interaction on glass densification under cold and shock compressions is assessed from MD simulations of silica glass under room and shock Hugoniot conditions, respectively. Results from these simulations indicate that the appearance of oxygen complexes (primarily pairs) interacting through soft-repulsive shoulder potential occurs at 8-10 GPa, and under cold compression conditions becomes notable at 40 GPa, essentially coinciding with the transition to a Si sixfold coordination state. An analysis of changes in system structure in compressed and shocked states reveals that the O ions interacting through the soft-repulsive shoulder potential in denser states of silica glass may create a mechanical multi-stability under elevated pressures and thus to contribute to the observed anomalous densification.     

Quantum effects on adsorption and diffusion of hydrogen and deuterium in microporous materials

Monte Carlo and molecular dynamics simulations and neutron scattering experiments are used to study the adsorption and diffusion of hydrogen and deuterium in zeolite Rho in the temperature range of 30-150 K. In the molecular simulations, quantum effects are incorporated via the Feynman-Hibbs variational approach. We suggest a new set of potential parameters for hydrogen, which can be used when Feynman-Hibbs variational approach is used for quantum corrections. The dynamic properties obtained from molecular dynamics simulations are in excellent agreement with the experimental results and show significant quantum effects on the transport at very low temperature. The molecular dynamics simulation results show that the quantum effect is very sensitive to pore dimensions and under suitable conditions can lead to a reverse kinetic molecular sieving with deuterium diffusing faster than hydrogen.     

TATB晶体结构的周期性密度泛函理论研究

对TATB晶体进行DFT-B3LYP/6-31G~(* *)周期性计算研究，求得其能带能带结 构和电子结构。探讨了结构-性能关系，从带隙约为4.1eV扒知TATB晶体的导电性处 于半导体和绝缘体之间，计算所得升华热为136.25kJ·mol~(-1)， 与实验值良好 相符，从原子间距和Mülliken集居分析，发现TATB晶体中同一层分子之间存在氢 键，而不同层之间距离较大，作用较弱，TATB分子中硝基氧带较多负电荷而氨基氢 带较多正电荷，这使TATB很难成为电子受体和给体，故化学上很稳定，考察晶体中 点电荷静电势，发现其在(001)面上的投影呈均匀分布，而在(100)和(010)面上的 揣影则有明显界面，表明同层分子间电子呈高度离域，异层之间相互作用极小，这 可解释TATB晶体沿c轴鼓胀以及受热循环后长大的各向异性和不可复原性等实验事 实。     

Molecular dynamics simulation of single wall carbon nanotubes polymerization under compression

Single wall carbon nanotubes (SWCNTs) often aggregate into bundles of hundreds of weakly interacting tubes. Their cross-polymerization opens new possibilities for the creation of new super-hard materials. New mechanical and electronic properties are expected from these condensed structures, as well as novel potential applications. Previous theoretical results presented geometric modifications involving changes in the radial section of the compressed tubes as the explanation to the experimental measurements of structural changes during tube compression. We report here results from molecular dynamics simulations of the SWCNTs polymerization for small diameter arm chair tubes under compression. Hydrostatic and piston-type compression of SWCNTs have been simulated for different temperatures and rates of compression. Our results indicate that large diameter tubes (10,10) are unlike to polymerize while small diameter ones (around 5 A) polymerize even at room temperature. Other interesting results are the observation of the appearance of spontaneous scroll-like structures and also the so-called tubulane motifs, which were predicted in the literature more than a decade ago.     

Molecular Mechanisms Causing Anomalously High Thermal Expansion of Nanoconfined Water

Anomalously high thermal expansion is measured in water confined in nanoscale pores in amorphous silica and the molecular mechanisms are identified by molecular dynamics (MD) simulations using an accurate dissociative water potential. The experimentally measured coefficient of thermal expansion (CTE) of nanoconfined water increases as pore dimension decreases. The simulations match this behavior for water confined in 30 Å and 70 Å pores in silica. The cause of the high expansion is associated with the structure and increased CTE of a region of water ～6 Å thick adjacent to the silica. The structure of water in the first 3 Å of this interface is templated by the atomically rough silica surface, while the water in the second 3 Å just beyond the atomically rough silica surface sits in an asymmetric potential well and displays a high density, with a structure comparable to bulk water at higher pressure.     

TATB基PBX结合能的分子动力学模拟

用分子动力学（MD）方法, 模拟计算了四种氟聚合物(聚偏二氟乙烯（PVDF）、聚三氟氯乙烯（PCTFE）、氟橡胶（F₂₃₁₁)、氟树脂(F₂₃₁₄))与TATB(1,3,5- 三氨基- 2,4,6- 三硝基苯)晶体的相互作用. 结果发现, 四种氟聚物与TATB的结合能大小排序为PVDF>F₂₃₁₁>F₂₃₁₄>PCTFE, 各氟聚物在TATB不同晶面上的结合能大小排序为(001)>(010)>(100), 结合能主要由分子间氢键决定.     

Coarse-grained potential models for structural prediction of carbon dioxide (CO2) in confined environments

In this paper, we propose coarse-grained single-site (CGSS), wall-CO(2), and CO(2)-CO(2) interaction potential models to study the structure of carbon dioxide under confinement. The CGSS potentials are used in an empirical potential based quasi-continuum theory, EQT, to compute the center-of-mass density and potential profiles of CO(2) confined inside different size graphite slit pores. Results obtained from EQT are compared with those obtained from all-atom molecular dynamics (AA-MD) simulations, and are found to be in good agreement with each other. Though these CGSS interaction potentials are primarily developed and parameterized for EQT, they are also used to perform coarse-grained molecular dynamics (CG-MD) simulations. The results obtained from CG-MD simulations are also found to be in reasonable agreement with AA-MD simulation results.     

偏氟乙烯/三氟氯乙烯交替共聚物在TATB表面吸附的分子动力学模拟

采用COMPASS力场和NVT正则系综的动力学模拟方法, 搭建了聚合度分别为10, 50和100的偏氟乙烯(VDF)/三氟氯乙烯(CTFE)交替共聚物, 对交替共聚物在1,3,5-三氨基-2,4,6-三硝基苯(TATB)的(0,0,1)晶面上的吸附和结构进行了分子动力学(MD)模拟. 结果表明, 在300～320 K温区, 聚合度为100的VDF/CTFE交替共聚物链对TATB晶体有理想的表面活性和吸附能力, 以train型构象平铺于TATB表面. 通过对聚合度为10的交替共聚物的多链体系在TATB表面吸附的MD模拟, 表明了VDF/CTFE交替共聚物具有非凝聚吸附的高表面活性特征. 对搭建的乙酸乙酯溶剂化的聚合度为50的VDF/CTFE交替共聚物在TATB晶体表面吸附的模拟, 实验证明了溶剂小分子能够降低共聚物链的吸附能力, 且链以tail型构象吸附于TATB表面.     

Brownian dynamics simulation of adsorbed layers of interacting particles subjected to large extensional deformation

We present Brownian dynamics simulations of the compression and expansion of monolayers adsorbed at a planar interface. The surface-active species are modelled as monodisperse spherical particles that can form particle-particle elastic bonds. The objective is to model the large compression and expansion of viscoelastic protein films investigated in Langmuir trough experiments. We determine the stress-strain response of the system and the associated microstructural changes induced by the large deformation of the interface as a function of particle adsorption energy, and bond breakability and stiffness. We also study the effect of the velocity of compression and the type of compression (uniaxial or homogeneous) on the mechanism of collapse of the adsorbed films. Furthermore, we present simulations on complex mixed systems containing both bond-forming particles (modelling protein) and nonbond-forming particles (modelling surfactant). We find that the preferential desorption of one type of particle or the other, upon compression, is sensitive to the extent of bond breakability of the bond-forming species.     

环四甲撑四硝胺/1,3,5-三氨基-2,4,6-三硝基苯共晶炸药的分子模拟研究

构建环四甲撑四硝胺 (HMX) /1,3,5-三氨基-2,4,6三硝基苯 (TATB)不同的共晶结构模型,用分子动力学(MD)模拟得到其平衡结构。基于平衡结构进行X射线粉末衍射（XRD）图谱模拟和能量计算。结果表明,与纯组分相比,HMX/TATB共晶结构的X射线粉末衍射图与主成分HMX相似,并均有新峰出现;TATB在HMX表面自由能最高、生长速率最慢的 (0 1 1) 晶面上发生取代后的能量最低,结构最稳定,据此推测在制备HMX/TATB共晶炸药过程中,TATB分子更容易进入HMX自由能高的晶面,得到结构稳定的共晶而使HMX变得更为钝感。     

Moisture desorption rates from TATB formulations: experiments and kinetic models

The rate of water desorption from PBX-9502, a formulation containing 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), is measured using temperature-programmed desorption and modeled using conventional kinetic modeling methods. The results of these studies show two stages of moisture release. At lower temperatures, the release is likely assisted by thermal expansion of the TATB and melting of the Kel-F binder. At higher temperatures, a considerable amount of water is released and is attributed to sublimation of the TATB, which exposes new surfaces for water desorption.     

Feature activated molecular dynamics: an efficient approach for atomistic simulation of solid-state aggregation phenomena

An efficient approach is presented for performing efficient molecular dynamics simulations of solute aggregation in crystalline solids. The method dynamically divides the total simulation space into "active" regions centered about each minority species, in which regular molecular dynamics is performed. The number, size, and shape of these regions is updated periodically based on the distribution of solute atoms within the overall simulation cell. The remainder of the system is essentially static except for periodic rescaling of the entire simulation cell in order to balance the pressure between the isolated molecular dynamics regions. The method is shown to be accurate and robust for the Environment-Dependant Interatomic Potential (EDIP) for silicon and an Embedded Atom Method potential (EAM) for copper. Several tests are performed beginning with the diffusion of a single vacancy all the way to large-scale simulations of vacancy clustering. In both material systems, the predicted evolutions agree closely with the results of standard molecular dynamics simulations. Computationally, the method is demonstrated to scale almost linearly with the concentration of solute atoms, but is essentially independent of the total system size. This scaling behavior allows for the full dynamical simulation of aggregation under conditions that are more experimentally realizable than would be possible with standard molecular dynamics.     

"Stubborn" triaminotrinitrobenzene: unusually high chemical stability of a molecular solid to 150 GPa

We report an unexpectedly high chemical stability of molecular solid 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) under static high pressures. In contrast to the high-pressure behavior of the majority of molecular solids, TATB remains both chemically stable and an insulator to 150 GPa--well above the predicted metallization pressure of 120 GPa. Single crystal studies have shown that TATB exhibits pressure-induced Raman changes associated with two subtle structural phase transitions at 28 and 56 GPa. These phase transitions are accompanied by remarkable color changes, from yellow to orange and to dark red with increasing pressure. We suggest that the high-stability of TATB arises as a result of its hydrogen-bonded aromatic two-dimensional (2D) layered structure and highly repulsive interlayer interaction, hindering the formation of 3D networks or metallic states.     

Investigating the relationship between infrared spectra of shared protons in different chemical environments: a comparison of protonated diglyme and protonated water dimer

The energetics, dynamics, and infrared spectroscopy of the shared proton in different chemical environments is investigated using molecular dynamics simulations. A three-dimensional potential energy surface (PES) suitable for describing proton transfer between an acceptor and a donor oxygen atom is combined with an all-atom force field to carry out reactive molecular dynamics simulations. The construction of the fully dimensional PES is inspired from the established mixed quantum mechanics/molecular mechanics treatment of larger systems. The "morphing potential" method is used to transform the generic PES for proton transfer along an O...H+...O motif into a three-dimensional PES for proton transfer in protonated diglyme. Using molecular dynamics simulations at finite temperature, the gas phase infrared spectra are calculated for both species from the Fourier transform of the dipole moment autocorrelation function. For protonated diglyme the modes involving the H+ motion are strongly mixed with other degrees of freedom. At low temperature, the O...H+...O asymmetric stretching vibration is found at 870 cm-1, whereas for H5O2+ this band is at 724 cm-1. As expected, the vibrational bands of protonated diglyme show no temperature dependence whereas for H5O2+ at T = 100 K the proton transfer mode is found at 830 cm-1, in good agreement with 861 cm-1 from very recent molecular dynamics simulations.