Tilt Of Molecules Research Articles

Optical anisotropy and surface phases of cholesterol derivative monolayer at air–water interface

Cholesterol and its derivatives play crucial roles in regulating processes of biological membranes. Langmuir monolayer can mimic a bio-membrane which can be used to investigate the molecular interaction governing the important physical phenomena. The cholesterol derivative exhibiting mesophases (CHLC molecules) was synthesized and spread at the air–water (A/W) interface to investigate the surface behavior. The monolayer exhibited a variety of surface phases such as gas, liquid expanded (LE), low density liquid like (L1) and liquid condensed (L2) phases. Treating the CHLC molecules to be rod-like, the average tilt of the molecules with respect to the surface normal in these phases are found to be different. The tilt angle decreases systematically from LE to L2 phase. The optical anisotropy of the ultrathin Langmuir-Blodgett (LB) films of CHLC molecules in these phases was measured using the surface plasmon resonance (SPR) spectroscopy. The high tilted molecules in the ultrathin LB film displayed a high value of optical anisotropy. The ultrathin film of CHLC molecules at different interfaces was investigated using Brewster angle microscopy, X-ray reflectivity (XRR), SPR spectroscopy and atomic force microscopy. This study is useful for the systems where the physical phenomena are governed by tilt of the molecules.

Orientation transitions and chiral assemblies of para-terphenyl molecules on Cd(0001).

The interplay between orientation transition and chiral self-assemblies of para-terphenyl (P3P) molecules on the Cd(0001) surface has been investigated using low temperature scanning tunneling microscopy and density functional theory calculations. Three distinct molecular orientations have been discerned from the self-assembled thin films of P3P. At the low coverage, flat-lying molecules appear in the homochiral domains with the incommensurate registry to the substrate. With the coverage increasing, the incoming molecules are incorporated into the first layer with edge-on orientation and form the self-assembled zigzag chains. The alternative arrangement of zigzag chains with opposite chirality leads to the formation of a c(4 × 2) superstructure, in which the tilted molecules exhibit orientational frustration and fuzzy noises. The analysis of the tunneling spectra reveals that the electronic structure of P3P layers is contingent upon the hybridization between the electronic states of P3P molecules and the Cd(0001) surface. These results provide important insights into the interplay between orientational transition and chiral assembly of P3P molecules on metal substrates.

Microscopic Analysis of the Water/Glycerol/EO30PS System in Bulk and on a Solid Substrate.

Surfactant systems are often employed in cosmetic formulations where they dry on skin as a surface, thereby becoming increasingly concentrated systems. To better understand this drying process, we focused on the difference of self-assembled structures of the water/glycerol/polyoxyethylene (30) phytosteryl ether (EO30PS) system in bulk and on a solid substrate because the interaction between the substrate and the surfactant may have a substantial effect on the self-assembly, which may be related to the bulk structure but in detail may also differ strongly from the bulk situation. In bulk, small-angle neutron scattering (SANS) experiments showed that with increasing loss of water, the degree of ordering increases but changes of the aggregate structure are rather small. The results indicate that ellipsoidal micelles of EO30PS are densely packed and simply become more ordered in bulk during the drying process. On the other hand, neutron reflectometry revealed that EO30PS molecules adsorb onto a Si surface in the form of bilayers and analysis indicates that at a high concentration (c = 20 wt %), there are on average two bilayers (a double bilayer) on the Si substrate. The adsorbed membrane structure of EO30PS is rather thin with respect to its hydrophobic part, indicating tilted molecules, containing only some solvent, and being not highly ordered. These experimental results then allow for a much deeper understanding of the structural properties of practical formulations as they are applied, for instance, in cosmetic lotions.

Tilt Modulus of Bilayer Membranes Self-Assembled from Rod-Coil Diblock Copolymers.

Quantitatively understanding membrane fission and fusion requires a mathematical model taking their underlying elastic degrees of freedom, such as the molecule's tilt, into account. Hamm-Kozlov's model is such a framework that includes a tilt modulus along with the bending modulus and Gaussian modulus. This paper investigates the tilt modulus of liquid-crystalline bilayer membranes by applying self-consistent field theory. Unlike the widely used method in molecular dynamics simulation which extracts the tilt modulus by simulating bilayer buckles with various single modes, we introduce a tilt constrain term in the free energy to stabilize bilayers with various tilt angles. Fitting the energy curve as a function of the tilt angle to Hamm-Kozlov's elastic energy allows us to extract the tilt modulus directly. Based on this novel scheme and focused on the bilayers self-assembled from rod-coil diblock copolymers, we carry out a systematic study of the dependence of the tensionless A-phase bilayer's tilt modulus on the microscopic parameters.

A one-dimensional high-order commensurate phase of tilted molecules.

We report on the formation of a high-order commensurate (HOC) structure of 5,14-dihydro-5,7,12,14-tetraazapentacene (DHTAP) molecules on the highly corrugated Cu(110)–(2 × 1)O surface. Scanning tunnelling microscopy shows that the DHTAP molecules form a periodic uniaxial arrangement in which groups of seven molecules are distributed over exactly nine substrate lattice spacings along the [1̄10] direction. DFT-calculations reveal that this peculiar arrangement is associated with different tilting of the seven DHTAP molecules within the quasi one-dimensional HOC unit cell. The orientational degree of freedom thus adds a new parameter, which can efficiently stabilize complex molecular structures on corrugated surfaces.

DFT study of chain length dependence of alkyl phosphonic acid molecules structure on Al[formula omitted]O[formula omitted] in pure and mixed monolayers

The geometrical structure of alkylphosphonic acid molecules on α-Al2O3 (0001) surface with different carbon chain lengths, at different coverages, in pure and mixed models, are investigated using density functional theory (DFT) calculations with optb86b van der Waals (vdW) corrections. Our calculations indicate a clear dependence of the structural characteristics of alkylphosphonic acid molecules on their chain length, and are consistent with previously reported experimental and theoretical results. We show that the orientation of molecules with short alkyl chain is principally forced by the anchor group, while the orientation of molecules with long chain is significantly influenced by the chain flexibility and the intermolecular interaction. This result is well confirmed when mixing short and long alkylphosphonic acid molecules. The mixed model was a useful choice for understanding the ordering of molecules. In the mixed model, we found a clear up-righting of molecules with short alkyl chains and of the bottom part of molecules with long alkyl chains (the part that corresponds to the length of the molecule with short alkyl chain). The up-righting of the small molecule relies to the interaction between the upper tail of long molecule and the short molecule, which in return, forces the bottom tail of long molecule to be more perpendicular to the substrate. However, this interaction causes an increase of the tilt angle of the upper tail of long alkyl chain molecules when the chain length difference is of twelve or eight carbon atoms. Since the adsorption energy depends on the geometrical structure, one can notice that, for more tilted molecules, at low coverage, a higher adsorption energy can be obtained. However, for less tilted molecules, at high coverage, we found a linear dependence of the adsorption energy to the chain length. In the former case, the molecule-substrate interaction is more prominent. However, for the latter case, the molecule-molecule interaction energy increases with increasing chain length. This theoretical study is useful to predict some advanced applications of pure and mixed monolayers in organic devices.

Surface Plasmon Resonance for In-Plane Birefringence Measurement of Anisotropic Thin Organic Film

The measurement of in-plane birefringence (\(\Delta {n}\)) of ultrathin film is challenging due to a significant deviation of physical properties of materials in ultrathin regime as compared to that in bulk state. Surface plasmon resonance (SPR) phenomenon can be employed to measure change in refractive index of ultrathin film at a very high resolution. This article discusses simulation of SPR phenomenon in Kretschmann configuration for the measurement of \(\Delta {n}\) in organic thin film exhibiting nematic-like ordering on the two-dimensional gold surface. The distribution of plasmonic field on the gold surface was found to be anisotropic. This suggested that the coupling plasmonic field with that of organic thin film exhibiting nematic-like ordering on the gold surface will be non-isotropic. Therefore, a nonzero difference in resonance angle (RA) was obtained from SPR measurement performed along the optic-axis (OA) and orthogonal to OA of the in-plane nematic ordering (\(\Delta \theta\)). A calibration surface showing the variation of (\(\Delta \theta\)) as a function of \(\Delta {n}\) and thickness of thin organic film consisting of shape anisotropic tilted molecules exhibiting nematic-like ordering on gold surface was obtained. This calibration surface was employed for the measurement of \(\Delta {n}\) of single layer of Langmuir–Blodgett films of cadmium stearate (CdSA) and 4’-octyl-4-biphenylcarbonitrile (8CB) deposited on SPR chips. The thickness of the LB films was estimated using X-ray reflectivity measurement, and \(\Delta \theta\) was measured using a home built SPR instrument. The \(\Delta {n}\) values were found to be 0.012 and 0.022 for ultrathin films of CdSA and 8CB molecules, respectively.

Molecular Chains: Arranging and Programming Logic Gates.

One particularly fascinating vision for charge-operated devices is the controlled assembly of structures from single surface-deposited molecules. Here, we report on the assembly of linear clusters that consist of phthalocyanine (H2Pc) molecules on a Ag(111) surface. The molecules are imaged as well as manipulated with a low-temperature scanning tunneling microscope (STM). Upon deprotonation of every second H2Pc, the resulting HPc molecule exhibits an isomeric bistability which can be used as inputs in logic gates. Combining our STM measurements with density functional theory calculations we show that the HPc isomers exhibit a repulsive electrostatic interaction with adjacent H2Pc molecules which, due to the asymmetric charge distribution on HPc, results in a counterclockwise or clockwise molecule tilt of the latter, thereby defining the logic 0 and 1 of the output. It is shown that information can be relayed along molecule chains over distances equivalent to at least nine molecules.

A two-state model for the modulated B7 liquid crystalline phase exhibited by bent-core molecules

Liquid crystals (LC) made of bent-core (BC) organic molecules have been intensively studied over the past two decades. The B7 LC consists of smectic layers in which tilted molecules have an in-plane polar packing, the polarization vector (P) having a splay distortion forming stripes of tens of nanometers in width, and undulated layers giving rise to 2D rectangular or oblique lattices. The prevailing phenomenological theory attributes this structure to a strong coupling between molecular tilt in the layers and divP. Based on our recent studies on other phases exhibited by BC molecules, we propose a new model in which the physical origin of the stripes arises from a minority (~10%) of the BC molecules having less bent excited state (ES) conformers which can freely rotate about their long axes, and aggregate to form smectic C type walls, in which the tilt angle is relatively small. The more bent ground state (GS) conformers with polar packing in turn form the splayed structure between such walls to lower the free energy. The mismatch in the layer spacing between the domains with ES and GS conformers generates the structures in the B7 phase described above. The model predicts a weak first order transition from B7 to the uniform B2 phase as the temperature is lowered, as experimentally observed in some compounds. We show that the observed slow increase of the stripe width in the LC to micrometer dimensions in free standing films can be attributed to changes in the physical parameters by chemical degradation and absorption of ions by the exposed polarized layers. We also describe different possible structures of the undulated layers, including a stacking of racemic pairs of SmCaPF layers within the stripes. Some possible methods of testing the model are also indicated.

Reversible Polymorphic Transition and Hysteresis-Driven Phase Selectivity in Single-Crystalline C8-BTBT Rods.

Organic semiconductors (OSCs) are highly susceptible to the formation of metastable polymorphs that are often transformed by external stimuli. However, thermally reversible transformations in OSCs with stability have not been achieved due to weak van der Waals forces, and poor phase homogeneity and crystallinity. Here, a polymorph of a single crystalline 2,7-dioctyl[1] benzothieno[3,2-b][1]benzothio-phene rod on a low molecular weight poly(methyl methacrylate) (≈120k) that limits crystal coarsening during solvent vapor annealing is fabricated. Molecules in the polymorph lie down slightly toward the substrate compared to the equilibrium state, inducing an order of greater resistivity. During thermal cycling, the polymorph exhibits a reversible change in resistivity by 5.5 orders with hysteresis; this transition is stable toward bias and thermal cycling. Remarkably, varying cycling temperatures leads to diverse resistivities near room temperature, important for nonvolatile multivalue memories. These trends persist in the carrier mobility and on/off ratio of the polymorph field-effect transistor. A combination of in situ grazing incident wide angle X-ray scattering analyses, visualization for electronic and structural analysis simulations, and density functional theory calculations reveals that molecular tilt governs the charge transport characteristics; the polymorph transforms as molecules tilt, and thereby, only a homogeneous single-crystalline phase appears at each temperature.

Structure of Langmuir Monolayers of Perfluorinated Fatty Acids: Evidence of a New 2D Smectic C Phase.

Due to the characteristic chain rigidity and weak intermolecular interactions of perfluorinated substances, the phase diagram of Langmuir monolayer formed by perfluorinated molecules has been interpreted so far as displaying only two phases, a 2D gas (G) and a liquid condensed (LC). However, in this work, we presented Grazing Incidence X-ray Diffraction measurements, which exhibit two diffraction peaks on the transition plateau: One is the signature of the hexagonal structure of the LC phase, the second one is associated to the low-density fluid phase and is thus more ordered than expected for a 2D gas or a typical fluid phase. Atomistic molecular dynamics simulations, performed on the transition plateau, revealed the existence of clusters in which domains of vertical molecules organized in a hexagonal lattice coexist with domains of parallel lines formed by tilted molecules, a new structure that could be described as a “2D smectic C” phase. Moreover, the diffraction spectrum calculated from the simulation trajectories compared favorably with the experimental spectra, fully validating the simulations and the proposed interpretation. The results were also in agreement with the thermodynamic analysis of the fluid phase and X-ray Reflectivity experiments performed before and after the transition between these two phases.

Origin of the band dispersion in a metal phthalocyanine crystal

Understanding the crystal structure and electronic states of the organic semiconductor is of fundamental importance for developing the materials for the organic electronics. However, the theoretical treatment of organic semiconductors remains challenging, as the semilocal density functional theory fails to describe the dispersion forces accurately. We use van der Waals inclusive density functionals to study the zinc phthalocyanine polymorphs. It is found that the structure and energetics are well described with the van der Waals density functional, and as a result, the electronic band structure is nicely reproduced. Furthermore, we reveal that the distance between the molecules and the molecule tilt angle are important factors that determine the electronic band dispersion.

Numerical Analysis of the Phase Birefringence of the Photonic Crystal Fibers Selectively Filled with Liquid Crystal

In this work, we present the theoretical investigation of the phase birefringence in a multi-component-glasses photonic crystal fiber, selectively infiltrated with various nematic liquid crystals. We compare the influence of different PCF infiltration patterns on the fiber phase birefringence. The ability to continuously tune birefringence up or down, depending on the direction of LC molecules tilt is also presented.

Origin of weak layer contraction in de Vries smectic liquid crystals.

Structural investigations of the de Vries smectic-A (SmA) and smectic-C (SmC) phases of four mesogens containing a trisiloxane end segment reveal a linear molecular conformation in the SmA phase and a bent conformation resembling a hockey stick in the SmC phase. The siloxane and the hydrocarbon parts of the molecule tilt at different angles relative to the smectic layer normal and are oriented along different directions. For the compounds investigated, the shape of orientational distribution function (ODF) is found to be sugarloaf shaped and not the widely expected volcano like with positive orientational order parameters: ⟨P2⟩ = 0.53-0.78, ⟨P4⟩ = 0.14-0.45, and ⟨P6⟩∼0.10. The increase in the effective molecular length, and consequently in the smectic layer spacing caused by reduced fluctuations and the corresponding narrowing of the ODF, counteracts the effect of molecular tilt and significantly reduces the SmC layer contraction. Maximum tilt of the hydrocarbon part of the molecule lies between approximately 18° and 25° and between 6° and 12° for the siloxane part. The critical exponent of the tilt order parameter, β∼0.25, is in agreement with tricritical behavior at the SmA-SmC transition for two compounds and has lower value for first-order transition in the other compounds with finite enthalpy of transition.

Epitaxial Growth of Pentacene on Alkali Halide Surfaces Studied by Kelvin Probe Force Microscopy

In the field of molecular electronics, thin films of molecules adsorbed on insulating surfaces are used as the functional building blocks of electronic devices. Control of the structural and electronic properties of the thin films is required for reliably operating devices. Here, noncontact atomic force and Kelvin probe force microscopies have been used to investigate the growth and electrostatic landscape of pentacene on KBr(001) and KCl(001) surfaces. We have found that, together with molecular islands of upright standing pentacene, a new phase of tilted molecules appears near step edges on KBr. Local contact potential differences (LCPD) have been studied with both Kelvin experiments and density functional theory calculations. Our images reveal that differently oriented molecules display different LCPD and that their value is independent of the number of molecular layers. These results point to the formation of an interface dipole, which may be explained by a partial charge transfer from the pentacene to the surface. Moreover, the monitoring of the evolution of the pentacene islands shows that they are strongly affected by dewetting: Multilayers build up at the expense of monolayers, and in the Kelvin images, previously unknown line defects appear, which reveal the epitaxial growth of pentacene crystals.

Molecular tilt near nanoparticles in the smectic-Aphase of a de Vries liquid-crystalline compound

We show how the inclusions of the nanoparticles or the clusters of nanoparticles in the liquid-crystalline smectic-A phase lead to layer deformations and may create a tilt in their vicinity, thus inducing locally a smectic-A-smectic-C transition. We have studied a freestanding film of "de Vries" compound, which exhibits the smectic-A-smectic-C transition without layer shrinkage, mixed with functionalized gold nanoparticles. The tilt induced by nanoparticle clusters, which decorate the edge dislocations, has been observed in the smectic-A phase. The tilt of liquid-crystal molecules near nanoparticles is a consequence of interaction of liquid-crystalline molecules with the surface of nanoparticles. The observed tilt may prove the concept of existence of a disordered tilt in the smectic-A phase of de Vries compounds. The tilt distribution near nanoparticles is discussed using both the smectic-A elasticity and local smectic-A-smectic-C transition.

Chiral domain formation from the mixture of achiral rod-like liquid crystal and tri boomerang-shaped molecule

Spontaneous formation of chiral domains such as a helical filament and a bent-broom texture was observed from the mixture of a rod-like liquid crystal octylcyano-biphenyl (8CB) and a tri boomerang-shaped 2,4,6-triphenoxy-1,3,5-triazine (triphenoxy) molecule. Although the constituent molecules were achiral, their mixture showed the chiral domains with the equal fraction of the opposite handedness. No tilt of 8CB molecules in the smectic layer was observed, implying the chirality is not due to the polar packing and tilt of the molecules. In addition, the splay and bend elastic constant of 8CB was decreased after doping triphenoxy. A structural conformation of triphenoxy and an orientational coupling between 8CB and triphenoxy are considered to be related to the chiral domain formation.

Spontaneous Change in Molecular Orientation at Order–Disorder Transition of Tetracene on Ag(111)

We investigate the molecular orientation of tetracene in ordered and disordered layers on Ag(111) using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Quantitative analysis of NEXAFS intensities reveals that the compact monolayer α-phase at 150 K consists of essentially flat-lying molecules with an average tilt angle α < 9° with respect to the Ag(111) surface. At room temperature the tetracene monolayer is dynamically disordered with α = 15 ± 4° (α′-phase). The increase in the average tetracene tilt angle indicates that orientational degrees of freedom perpendicular to the surface drive the order–disorder transition in the tetracene monolayer on Ag(111). We argue that the phase transition can be explained by a delicate balance between the interfacial enthalpy and the orientational entropy. Furthermore, we suggest that tetracene/Ag(111) may be a good example of Onsager’s system of nonattracting rigid anisotropic objects (so-called “hard rods”) in two dimensions. On the other hand, the complex bilayer β-phase at 150 K includes tilted molecules with α ≈ 36°, in good agreement with the structure model introduced by Soubatch et al. [Phys. Rev. B 2011, 84, 195440]. This demonstrates that, under the influence of a second layer, π-conjugated molecules in contact with a metal surface can tilt out of the surface plane.

Ordered and disordered packing of coronene molecules in carbon nanotubes

Monte Carlo simulations of coronene molecules in single-walled carbon nanotubes (SWCNTs) and dicoronylene molecules in SWCNTs are performed. Depending on the diameter D of the encapsulating SWCNT, regimes favoring the formation of ordered, one-dimensional (1D) stacks of tilted molecules (D ≤ 1.7 nm for coronene@SWCNT, 1.5 nm ≤ D ≤ 1.7 nm for dicoronylene@SWCNT) and regimes with disordered molecular arrangements and increased translational mobilities enabling the thermally induced polymerization of neighboring molecules resulting in the formation of graphene nanoribbons (GNRs) are observed. The results show that the diameter of the encapsulating nanotube is a crucial parameter for the controlled synthesis of either highly ordered 1D structures or GNR precursors.

Liquid Crystals at Interfaces

AbstractThe ordering in liquid crystals (LCs) can be influenced by an interface. Some of these molecules adsorbed at the air‐water interface yield a stable Langmuir monolayer. They exhibit numerous surface phases, which are classified on the basis of intermolecular separation and ordering. These surface phases are governed by the molecular interactions and the ambient experimental conditions such as temperature, humidity, pH, and ion content of the subphase. In this article, the role of molecular interactions on the surface behavior of several rodlike LCs are discussed. The Langmuir monolayer of a cholesteric LC exhibits an interesting low density liquid (L1′) phase with tilted molecules. Brewster angle microscopy reveals stripe patterns, which arise due to the precession of the tilted molecules. It is demonstrated that this molecular precession can be controlled by the relative humidity, presence of cations in the subphase, and incorporation of appropriate molecular species. The Langmuir monolayer and Langmuir‐Blodgett films of a novel rod‐disc hybrid LC are discussed.