Azobenzenes as light-controlled molecular electronic switches in nanoscale metal-molecule-metal junctions

Conductance switching associated with the photoisomerization of azobenzene-based (Azo) molecules was observed in nanoscopic metal-molecule-metal junctions. The junctions were formed by using a conducting atomic force microscope (C-AFM) approach, where a metallic AFM tip was used to electrically contact a gold-supported Azo self-assembled monolayer. The measured 30-fold increase in conductance is consistent with the expected decrease in tunneling barrier length resulting from the conformational change of the Azo molecule.     

Molecular switch on a metal surface

We report a theoretical study for the conformational switching of molecules on Au(111) surface in the presence of an applied electric field. Ab initio calculations for N-(2-mercaptoethyl)benzamide indicate that this molecule, when adsorbed, can exist as two stable conformers of nearly equal energies, but the dipoles point in reverse directions with respect to the surface. An electric field can be used to "switch" one conformer to the other, and during this process, there is an abrupt change in the height of the molecule from the surface. This change is expected to cause a conductance switching in the system. Further calculations for N-(2-mercaptoethyl)-4-phenylazobenzamide suggest that the experimentally observed phase switching of this molecule is associated with a conformational change accompanied by dipole reversal.     

Exploring the possibilities to control the molecular switching properties and dynamics: A field-switchable rotor-stator molecular system

A bistable, dipolar stator-rotor molecular system-candidate for molecular electronics is investigated. We demonstrate that it is possible to control the intramolecular torsional states and dynamics in this system by applying an appropriate additional electric field (instead of biasing one), achieving fine tuning and modulation of the relevant properties. The electric field effects on the quantities responsible for torsional dynamics (potential energy surface, potential barrier height, quantum and classical transition probabilities, correlation time, HOMO-LUMO gap) are studied from first principles. Our results indicate that it is possible to artificially stabilize the metastable conformational state of the studied molecule. The importance of this is evident, as the current-voltage characteristics of the metastable state are clearly distinguishable from the current-voltage characteristics of the two stable states. We report for the first time exact calculations related to the possibilities to control the thermally induced stochastic switching, and reduce the noise in a practical application. Thus, we believe that the molecule studied in this paper could operate as a field-switchable molecular device under real conditions.     

Supramolecular Assembly and Headgroup Effect in Interfacial Organized Films (I): A Study of Some Bolaamphiphiles

Two bola form Schiff bases derivatives with different substituted head groups have been designed and their interfacial phase behaviors and coordination with Cu(II) ions were investigated. It has been found that while one molecule with benzene headgroup formed dotted aggregations at the air/water interface, another with naphthyl moiety as head group formed crystalline multilayer films on water surface. When on the sub phase containing Cu(II) ions, both of the Schiff bases can coordinate with Cu(II) in situ in the spreading films with the obvious conformational change of alkyl chains. The in situ Cu(II)-coordinated films could be transferred onto solid substrates and subsequently characterized by various spectroscopic methods such as UV-vis and Fourier transform infrared spectra as well as the morphological character with atomic force microscopy measurement. In comparison, the ex situ coordination process at the liquid/solid interface have also been investigated by continuous spectral measurement. Depending on the different head groups, these amphiphiles showed different aggregation behaviors in the Langmuir-Blodgett films. Particularly, during the coordination process of ligand with Cu(II) ions in organized molecular films, great conformational change of the alkyl chains was observed. At the same time, a rational explanation about the head group effect on regulating the aggregation behaviors was discussed.     

Roles of entropic and solvent damping forces in the dynamics of polymer tethered nanoparticles and implications for single molecule sensing

Tethering a particle to a surface with a single molecule allows detection of the molecule and analysis of molecular conformations and interactions. Understanding the dynamics of the system is critical to all applications. Here we present a plasmonic imaging study of two important forces that govern the dynamics. One is entropic force arising from the conformational change of the molecular tether, and the other is solvent damping on the particle and the molecule. We measure the response of the particle by driving it into oscillation with an alternating electric field. By varying the field frequency, we study the dynamics on different time scales. We also vary the type of the tether molecule (DNA and polyethylene glycol), size of the particle, and viscosity of the solvent, and describe the observations with a model. The study allows us to derive a single parameter to predict the relative importance of the entropic and damping forces. The findings provide insights into single molecule studies using not only tethered particles, but also other approaches, including force spectroscopy using atomic force microscopy and nanopores.     

n-Si/TiO2/偶氮颜料微纳米尺度下的光生电荷转移性质

本文利用KFM 研究了n-Si/TiO₂/偶氮类颜料微纳米尺度下的光生电荷转移性质, 为进一步理解光电活性体系工作的微观机理提供了依据.     

Numerical coupled Liouville approach: Application to second hyperpolarizability of molecular aggregate

In our previous study [Int. J. Quant. Chem., to appear], we have developed a novel numerical calculation scheme for a dynamics of quantum network for linear molecular aggregates under intense time‐dependent electric fields. In this approach, each molecule is assumed to be an electric dipole arranged linearly with an angle from the longitudinal axis, and the molecular interactions are taken into account by adding the radiations from these dipoles to the external electric fields. The effects of the radiations from all the dipoles involve the intermolecular distance, the speed of light, retarded polarization, and its first‐ and second‐order time derivatives at the position of each dipole. The quantum dynamics is performed by solving coupled Liouville equations composed of the Liouville equation for each dipole. In the present study, we develop a calculation approach of nonperturbative second hyperpolarizability γ in our novel approach and examine the γ of dimer models composed of two‐state molecules under the one‐photon near resonant intense laser fields. Similar phase transition‐like behavior in the field‐intensity dependence of the γ is observed. We also investigate the second hyperpolarizability spectra in the three‐photon resonant region for dimers composed of three‐state molecules, which mimic the electronic states of allyl cation. Contrary to the one‐photon resonant case, phase transition‐like behavior is not observed in the intensity dependence of γ in the three‐photon resonant region. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 295–306, 1999     

Polymer matrix dependence of conformational dynamics within a π-stacked perylenediimide dimer and trimer revealed by single molecule fluorescence spectroscopy

The conformation of embedded molecule in a polymer matrix is sensitive to the local nano-environment that the molecule experiences. Particularly, single molecule spectroscopic methods have been utilized to visualize each molecular conformation in local sites of the polymer matrix by monitoring rotational diffusion and fluctuating fluorescence of the molecule. Here, we have performed single molecule spectroscopic experiments on a π-stacked perylenediimide (PDI) dimer and trimer, in which enhanced π-π interaction in π-stacked PDIs makes the fluorescence lifetime longer, embedded in two different polymers, namely poly(methyl methacrylate) (PMMA) and poly(butyl methacrylate) (PBMA), to reveal the conformational change depending on the polymer matrix. The fluorescence lifetimes of π-stacked PDIs are influenced by polymer surroundings because their molecular conformations are dependent on their interactions with the local environment in the polymer matrix. Furthermore, from an in-depth analysis of autocorrelation functions of fluorescence intensity trajectories, we could assign that the first autocorrelation value (lag 1) is larger as the intensity trace becomes more fluctuating. Thus, we expect that π-stacked PDIs, a model system for the formation of PDI excimer-like states, can be utilized to probe the surrounding nano-environment by monitoring the conformational change in real time.     

Conformational polymorphism and thermochemical analysis of 5,5' '-bis[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)ethyl]-2,2':5',2' ':5' ',2' '-quaterthiophene

The titled compound exists as two polymorphic solid phases (denoted form-I and form-II). Form-I obtained by as-synthesized material is a more stable phase. Form-II is a less stable phase. Spontaneous solid-solid transformation from form-II to form-I is observed in the temperature range between room temperature and the melting point of form-I (Tm = 156.5 degrees C), and its activation energy is estimated to be 96 kJ mol-1 by Arrhenius plot. The solid-solute-solid transformation (recrystallization from solution) from form-II to form-I is also observed. In contrast, form-II is obtained only by a solid-melt-solid transformation from form-I. Therefore, the system of two polymorphs is monotropic. The solid-state NMR measurement shows that form-I has the molecular conformation of complete S-syn-anti-syn in the oligothiophene backbone, whereas form-II has that of S-all-anti. With the solution NMR data, the polymorphism could not be observed. Therefore, the polymorphs originate from the different molecular packing involving the conformational change of the molecule. This unique property is attributed to the extra bulky terminal groups of the compounds. However, despite the extra bulky terminal groups, the mentioned polymorphism is not observed in the titled compound analogue which has S-all-anti conformation (like form-II).     

强外电场作用下二甲基硅酮的分子结构和激发态

The ground states of dimethyl siloxane under different intense electric fields ranging from - 0. 04 to 0. 04 a. u. are optimized using density functional theory DFT / B3P86 at 6-311 ++ G（d,p）level. The excitation energies and oscillator strengths under the same intense applied electric fields are calculated employing the revised hybrid CIS-DFT method. The result shows that the electronic state,molecular geometry,total energy,dipole moment and excitation energy are strongly dependent on the field strength and behave asymmetry to the direction of the applied electric field. As the electric field changes from - 0. 04 to 0. 04 a. u. ,the bond length of Si-O increases whereas the bond length of Si-C decreases because of the charge transfer induced by the applied electric field. The dipole moment of the ground state decreases linearly with the applied field strength. However,the dipole moment of molecule changes from positive to negative as the inverse electric field increase to - 0. 03 a. u. Further increase of the inverse electric field results in an increase of the total energy of the molecule. The dependence of the calculated excitation energies on the applied electric field strength is fitting well to the relationship proposed by Grozema. The excitation energies of the first five excited states of dimethyl siloxane decrease as the applied electric filed increases because the energy gap between the HOMO and LUMO become close with the field,which shows that the molecule is easy to be excited under electric field and hence can be easily dissociated.     

"分子行走理论"模型——分子熵的笼敝效应及其在有机酸碱性比较中的应用

基团的电子、共轭、超共轭、空间位阻、溶剂化等效应在有机酸碱理论及酸碱性分析中一直占据主导地位.但在气相状态下,分析某些物质的酸碱性时单用上述理论远不能满足要求,得不到与实验事实相符的结果.从热力学及分子统计力学角度出发,以量子化学为辅助,研究了分子熵值及其构象改变对物质酸碱性、反应活性、反应速率的影响.提出理想状态下"分子自由行走"、"自由均方行走距"等假设,并以此演绎出理想状态下有机分子构象改变所遵循的统计规律——"类自由结合链高斯模型".建立了"分子熵效应笼敝扩散"分子构象模型,用该理论成功解释了气相状态下甲、乙、丙、丁、戊、己酸酸性大小差异及气相氨、伯胺、仲胺、叔胺、苯胺、二苯胺的碱性差异.结果表明:自由均方行走距及分子笼敝大小是影响物质活性的关键因素.     

Combined vibrational,conformational energy and electron diffraction studies of trans-2-decalone

The structure of trans-2-decalone was investigated by combined gas phase electron diffraction, conformational energy and vibrational analyses. In this study first the minimum energy conformations for trans-2-decalone were calculated by molecular mechanics techniques using a force field described in the literature; the same field and the minimum energy conformations were then used in subsequent vibrational analyses to calculate the mean amplitudes of vibration for each minimum energy conformation of trans-2-decalone; these mean amplitudes and the corresponding internuclear distances were then used to calculate theoretical electron diffraction radial distribution curves which were compared to the experimental curves. Four conformational energy minima were investigated with one or both rings in a chair or non-chair form. The results of the combined investigations indicate that the molecule exists in the conformation which has both rings in a distorted chair form.     

Conformational analysis by UV spectroscopy: the decisive contribution of environment-induced electronic Stark effects

UV chromophores are frequently used as probes of the molecular structure. In particular, they are sensitive to the electric field generated by the molecular environment, resulting in the observation of Stark effects on UV spectra. While these environment-induced electronic Stark effects (EI-ESE) are already used for conformational analysis in the condensed phase, this work explores the potential of such an approach when performed at much higher conformational resolution in the gas phase. By investigating model alkali benzylacetate and 4-phenylbutyrate ion pairs, where the electric field applied to the phenyl ring is chemically tuned by changing the nature of the alkali cation, this work demonstrates that precise conformational assignments can be proposed based on the correlation between the conformation-dependent calculated electric fields and the frequency of the electronic transitions observed in the experimental UV spectra. Remarkably, the sole analysis of Stark effects and fragmentation patterns in mass-selected UV spectra provided an accurate and complete conformational analysis, where spectral differences as small as a few cm⁻¹ between electronic transitions were rationalized. This case study illustrates that the identification of EI-ESE together with their interpretation at the modest cost of a ground state electric field calculation qualify UV spectroscopy as a powerful tool for conformational analysis.

The correlation between experimental electronic transitions and calculated electric fields leads to precise conformational assignments and opens up the possibility of interpreting electronic spectra in a quantitative manner at the wavenumber scale.     

An atomic force microscopic investigation of electro-sensitive polymer surface

An electro-sensitive poly(2-acrylamide-2-methylpropane sulfonic acid) (PAMPS) film was fabricated by surface-initiated atom transfer radical polymerization (ATRP) method on silicon substrate. Atomic force microscopy (AFM) experiments in contact mode show that friction force and the adhesion force between the AFM tip and the film may change regularly with the alteration of the applied negative bias voltage between them, indicating that the microscopic wettability of the film can be adjusted by external electric field. On the other hand, the AFM experiments in tapping mode reveal that the film may take corresponding phase change under the electric field. These effects were considered to result from the conformational overturn of the sulfonic groups and the adjacent alkyl chains in the electric field.     

Up/Down Tuning of Poly(ionic liquid)s in Aqueous Two-Phase Systems

Thermally induced reversible up/down migration of poly(ionic liquid)s (PILs) in aqueous two-phase systems (ATPSs) was achieved for the first time in this study. Novel ATPSs were fabricated using azobenzene (Azo)- and benzyl (Bn)-modified PILs, and their upper and lower phases could be easily tuned using the grafting degree (GD) of the Azo and Bn groups. Bn-PIL with higher GD_Bn could go up into the upper phase and Azo-PIL come down to the lower phase when the temperature increased (>65 °C); this behavior was reversed at lower temperatures. Moreover, a reversible two-phase/single-phase transition was realized under UV irradiation. Experimental and simulation results revealed that the difference in the hydration capacity between Bn-PIL and Azo-PIL accounted for their unique phase-separation behavior. A versatile platform for fabricating ATPSs with tunable stimuli-responsive behavior can be realized based on our findings, which can broaden their applications in the fields of smart separation systems and functional material development.     

Molecules in an electric field: Some structural and spectroscopic consequences

It is theoretically shown that under the influence of an appropriately directed external electric field (ε) in H₂CO or a similar molecule (of the XYC = O type), the barrier to planar inversion in the ³n π* state decreases as the field strength increases. The molecule assumes a forced planar geometry in the ³n π* state rather abruptly when ε_(applied) > ε_(critical). This phenomenon of field-induced change of structure of an isolated molecule has the attributes of a first order phase transition. The effects should be spectroscopically detectable in the inversion spectrum. The existence of another critical field strength at which the molecule makes a more or less continuous transition from the normal convalent to a purely ionic structure is demonstrated and rationalized through a simple model.     

Molecular Dynamics Simulation: Influence of External Electric Field on Bubble Interface in Air Flotation Process

Molecular dynamics(MD) simulation was performed to investigate the influence of external electric field on the vapour-liquid interface of the bubble during the process of toluene separation by air flotation. The physicochemical properties of vapour-liquid interface, surface tension, probability of a hydrogen bonding near the vapour-liquid interface and the viscosity of liquid phase caused by external electric field were analyzed. The results show that the angle between the water molecule dipole moment and the normal z axis in the vapour phase changes smaller when the external electric field is applied. The surface tension and the probability of hydrogen bonding near the vapour-liquid interface increase with the increase of electric field strength. And the viscosity also increases under an external electric field. The results confirm that the external electric field has a positive effect on the performance of bubbles in air flotation, which may provide useful guidance for the combination of electric field and air flotation technology.     

Multiscale modelling of mesoscopic phenomena triggered by quantum events: light-driven azo-materials and beyond

The macroscopic functionality of soft (bio-)materials is often triggered by quantum-mechanical events which are highly local in space and time. In order to arrive at the resulting macroscopically observable phenomena, many orders of magnitude need to be bridged on both the time and the length scale. In the present paper, we first introduce a range of simulation methods at different scales as well as theoretical approaches to form bridges between them. We then outline a strategy to develop an adaptive multiscale simulation approach which connects the quantum to the mesoscopic level by bringing together ab initio molecular dynamics (QM), classical (force field) molecular dynamics (MM), and coarse grained (CG) simulation techniques. With a multitude of photoactive materials in mind, we apply our methodology to a prototypical test case-light-induced phase transitions in a liquid crystal containing the azobenzene photoswitch.     

外电场作用下甲基乙烯基硅酮分子结构和电子光谱

采用密度泛函B3P86方法在6-311++G(d, p)基组水平上优化得到了沿分子轴方向不同外电场(0-0.04 a.u.)作用下, 甲基乙烯基硅酮分子的基态电子状态、几何结构、电偶极矩和分子总能量. 在优化构型下利用杂化CIS-DFT方法(CIS-B3P86)研究了同样外电场条件下对甲基乙烯基硅酮的激发能和振子强度的影响. 计算结果表明, 分子几何构型与电场大小呈现强烈的依赖关系, 分子偶极矩μ随电场的增加先减小后急剧增大. 电场为零时, 分子总能量为-483.5532137 a.u., 随着电场增加, 能量升高, 在F=0.02 a.u.时达到最大值-483.5393952 a.u., 此后, 继续增大电场系统总能量则开始降低. 激发能随电场增加急剧减小, 表明在电场作用下, 分子易于激发和离解.