Molecular Orientational Dynamics Research Articles

Exploring the Impact of Intermolecular Interactions on the Glassy Phase Formation of Twist-Bend Liquid Crystal Dimers: Insights from Dielectric Studies

The formation of the nematic to twist-bend nematic (NTB) phase has emerged as a fascinating phenomenon in the field of supramolecular chemistry, based on complex intermolecular interactions. Through a careful analysis of molecular structures and dynamics, we elucidate how these intermolecular interactions drive the complex twist-bend modulation observed in the NTB. The study employs broadband dielectric spectroscopy spanning frequencies from 10 to 2 × 109 Hz to investigate the molecular orientational dynamics within the glass-forming thioether-linked cyanobiphenyl liquid crystal dimers, namely, CBSC7SCB and CBSC7OCB. The experimental findings align with theoretical expectations, revealing the presence of two distinct relaxation processes contributing to the dielectric permittivity of these dimers. The low-frequency relaxation mode is attributed to an “end-over-end rotation” of the dipolar groups parallel to the director. The high-frequency relaxation mode is associated with precessional motions of the dipolar groups about the director. Various models are employed to describe the temperature-dependent behavior of the relaxation times for both modes. Particularly, the critical-like description via the dynamic scaling model seems to give not only quite good numerical fittings, but also provides a consistent physical picture of the orientational dynamics in accordance with findings from infrared (IR) spectroscopy. Here, as the longitudinal correlations of dipoles intensify, the m1 mode experiences a sudden upsurge in enthalpy, while the m2 mode undergoes continuous changes, displaying critical mode coupling behavior. Interestingly, both types of molecular motion exhibit a strong cooperative interplay within the lower temperature range of the NTB phase, evolving in tandem as the material’s temperature approaches the glass transition point. Consequently, both molecular motions converge to determine the glassy dynamics, characterized by a shared glass transition temperature, Tg.

Dielectric Study of Liquid Crystal Dimers: Probing the Orientational Order and Molecular Interactions in Nematic and Twist-Bend Nematic Phases.

Dielectric spectroscopy in frequencies that range from 10 Hz to 1 GHz has been used to study the molecular orientational dynamics of the two types of dimers that form the twist-bend nematic phase over a wide range of temperatures for both nematic and twist-bend nematic phases. The symmetrical and asymmetrical liquid crystal dimers with the cyanobiphenyl mesogenic groups were investigated. The results were analyzed within the framework of the molecular theory of dielectric permittivity for nematogens. The two molecular processes can be assigned to the reorientation of the monomeric unit: the high frequency one to the precessional rotation of the longitudinal components of the cyanobiphenyl groups (CN) and the second (low frequency) to the end-over-end rotation of the CN dipole around the short molecular axis. The precession mode, which is determined by the local order and is almost unaffected by the phase transition from the nematic to the twist-bend phase, while the end-over-end rotation clearly slowed down at the transition, as it is affected by the growth of the intermolecular interactions. The latter corresponds well to the fact revealed by IR spectroscopy about the longitudinal correlation of the molecular dipoles.

Molecular Orientation and Energy Transfer Dynamics of a Metal Oxide Bound Self-Assembled Trilayer.

Self-assembly of molecular multilayers via metal ion linkages has become an important strategy for interfacial engineering of metalloid and metal oxide (MOx) substrates, with applications in numerous areas, including energy harvesting, catalysis, and chemical sensing. An important aspect for the rational design of these multilayers is knowledge of the molecular structure-function relationships. For example, in a multilayer composed of different chromophores in each layer, the molecular orientation of each layer, both relative to the adjacent layers and the substrate, influences the efficiency of vectorial energy and electron transfer. Here, we describe an approach using UV-vis attenuated total reflection (ATR) spectroscopy to determine the mean dipole tilt angle of chromophores in each layer in a metal ion-linked trilayer self-assembled on indium-tin oxide. To our knowledge, this is the first report demonstrating the measurement of the orientation of three different chromophores in a single assembly. The ATR approach allows the adsorption of each layer to be monitored in real-time, and any changes in the orientation of an underlying layer arising from the adsorption of an overlying layer can be detected. We also performed transient absorption spectroscopy to monitor interlayer energy transfer dynamics in order to relate structure to function. We found that near unity efficiency, sub-nanosecond energy transfer between the third and second layer was primarily dictated by the distance between the chromophores. Thus, in this case, the orientation had minimal impact at such proximity.

Molecular orientation dynamics triggers ferroelectricity and ferroelasticity in an organic–inorganic halide material

Ingenious molecular orientation dynamics achieves ferroelectricity and ferroelassticity in an organic–inorganic halide material with unique 1D corner-sharing lead bromide skeleton.

Molecular Orientation and Femtosecond Electron Transfer Dynamics in Halogenated and Nonhalogenated, Eco-Friendly Processed PTB7-Th, ITIC, PTB7-Th:ITIC, and PTB7-Th:PCBM Films

Molecular Orientation and Femtosecond Electron Transfer Dynamics in Halogenated and Nonhalogenated, Eco-Friendly Processed PTB7-Th, ITIC, PTB7-Th:ITIC, and PTB7-Th:PCBM Films

Spectroscopic study of D1–A–D2–A terpolymer films for optoelectronic applications

Several strategies have been considered in search of more efficient organic materials for charge transfer in photovoltaic devices. Among them, the integration of donor-acceptor (D-A) functional units on a conjugated copolymer has been widely applied. In this framework, we evaluated four terpolymers made up of donor moieties derived from 9,9-dioctylfluorene and 9-(heptadecan-9-yl)-9H-carbazole combined with 2,1,3-benzothiadiazole, the acceptor moiety, in different monomer ratios and polymerization routes (block and random microstructures). The preferred molecular orientation and charge transfer dynamics of the polymeric films were assessed by near edge X-ray absorption fine structure spectroscopy (NEXAFS) and resonant Auger electron spectroscopy (RAES) around the sulfur K-edge. Charge transfer times (τCT) were estimated by the Core-Hole Clock (CHC) method. Films with a high degree of organization were identified for the block terpolymer and random terpolymers with uneven amounts of donor units, showing a preferred orientation of the benzothiadiazole (BT) molecular plane parallel to the substrate surface. The values of τCT measured for all terpolymers were higher than those for typical polymers used in photovoltaic devices, which is not desirable for this type of optoelectronic application, but this may be correlated to the strong acceptor character of BT, the unit probed. To investigate the effect of film formation on the excited state behavior, steady-state and time-resolved photoluminescence measurements were also conducted. X-ray photoelectron spectroscopy (XPS) was employed to characterize the surface chemical composition of the terpolymer films. Based on the spectroscopic data the block copolymer appears to be the most suitable for the desired application.

Model-free analysis of molecular orientation in amorphous organic semiconductor films for understanding its formation dynamics: Methods and systematic investigation

To achieve high-performance organic light-emitting diodes (OLEDs), various amorphous organic semiconductor materials were developed, and the higher-order structure of their films and their formation dynamics were investigated. In particular, their molecular orientations were widely analyzed because it significantly affects optical and electrical properties of the OLEDs. However, conventional methods of the analysis of the orientation order parameter ( S ) need the construction of an anisotropic optical model, which brings a certain degree of analytical error and thus makes it difficult to assess the slight changes in S values arising from differences in experimental conditions. In this study, we present a simple model-free analytical method to estimate S values, named "QACIOS", that avoids the significant analytical errors and applies to various OLED materials, including materials that easily crystallize. In applying the method to UV/visible and IR spectral regions, the S values of electronic and vibrational transition dipole moments in the films can be simply estimated. The orientations of functional groups in single-layer and multilayer samples are obtainable separately, and in situ measurements are also demonstrated. Furthermore, we present a systematic analysis of the dependence of S on experimental conditions during sample fabrication such as deposition rate, substrate temperature, and substrate surface. From this analysis, the difference in formation dynamics of the molecular orientation of two structural isomers of OLED materials is quantitatively clarified, further demonstrating the usefulness of the method. A model-free simple analytical method by quantitative absorbance comparison with an isotropically oriented standard (QACIOS) is applied to systematic investigation of orientations of long molecular axis and functional groups in amorphous organic semiconductor films and their formation dynamics. • A model-free simple analytical method for reliable estimation of orientation order parameter is proposed and applied to many kinds of amorphous OLED materials. • Orientation analysis of functional groups in single-layer and multilayer samples are performed. • The difference in formation dynamics of molecular orientation of two OLED isomers is clarified quantitatively. • The method can be a commonly-used standard method for orientation analysis of OLED films.

Single-Shot Quantitative Polarization Imaging of Complex Birefringent Structure Dynamics.

Polarization light microscopes are powerful tools for probing molecular order and orientation in birefringent materials. While a number of polarization microscopy techniques are available to access steady-state properties of birefringent samples, quantitative measurements of the molecular orientation dynamics on the millisecond time scale have remained a challenge. We propose polarized shearing interference microscopy (PSIM), a single-shot quantitative polarization imaging method, for extracting the retardance and orientation angle of the laser beam transmitting through optically anisotropic specimens with complex structures. The measurement accuracy and imaging performance of PSIM are validated by imaging a birefringent resolution target and a bovine tendon specimen. We demonstrate that PSIM can quantify the dynamics of a flowing lyotropic chromonic liquid crystal in a microfluidic channel at an imaging speed of 506 frames per second (only limited by the camera frame rate), with a field-of-view of up to 350 × 350 μm2 and a diffraction-limit spatial resolution of ~2 μm. We envision that PSIM will find a broad range of applications in quantitative material characterization under dynamical conditions.

A constitutive model for strain hardening behavior of predeformed amorphous polymers: Incorporating dissipative dynamics of molecular orientation

A series of uniaxial compression tests are performed on amorphous thermoplastics poly (ethylene terephthalate)-glycol (PETG). The stress response shows a dramatic change with temperature and strain rate, including the modulus, yield strength and strain hardening. The strain hardening behavior also shows a strong dependence on predeformation, representing as a less pronounced hardening response during the reloading process with increasing the predeformation temperature and decreasing the predeformation rate. This phenomenon cannot be described by the models assuming a temperature-dependent hardening modulus. In this work, we develop a thermodynamic consistent model, which employs a dissipative back-stress tensor for molecular orientation. With increasing temperature, a stronger relaxation occurs, resulting in less molecular orientation and hardening response. A numerical scheme is also constructed to determine the model parameters. Comparison with experiments shows that the model is able to reproduce all the main features of the stress response at various strain rates spanning the glass transition region. The model can also accurately capture the strain hardening response of polymers predeformed to a strain of 30% or 60% at various temperatures and rates.

Molecular orientation and femtosecond charge transfer dynamics in transparent and conductive electrodes based on graphene oxide and PEDOT:PSS composites.

The conducting polymer, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), is certainly one of the most important substitute materials for indium tin oxide in organic devices. Its metallic conductivity and transmittance bring favorable perspectives for organic photovoltaic applications. Although graphene oxide (GO) is not a good conductor, it can form high-quality thin films and can be transparent, and additionally, GO is an inexpensive material and can be easily synthesized. This study investigated how the conductivity of a composite film of graphene oxide (GO) and different amounts of PEDOT:PSS can be modified. The effects of GO:PEDOT:PSS composites with several PEDOT:PSS proportions were analyzed in regards to the composite molecular structure and ordering, charge transfer dynamics (in the femtosecond range), electrical properties and morphology. For the best conductivity ratio GO found with 5% PEDOT:PSS, a solvent treatment was also performed, comparing the resistivity of the film when treated with dimethyl sulfoxide (DMSO) and with ethylene glycol.

Improving molecular orientation by optimizing relative delay and intensities of two-color laser pulses

We numerically explore molecular orientation dynamics with moderately intense nanosecond two-color laser pulses. It is believed that the nanosecond two-color pulse can adiabatically control the molecular orientation. However, in our simulation based on the time-dependent Schr\odinger equation, which naturally includes nonadiabatic effects, the orientation dynamics shows clear deviations from the adiabatic approximation (AA) results, while the molecular alignment dynamics is in good agreement with the AA results. The nonadiabaticity is significantly influenced by three parameters, the intensities, and the relative delay of the two wavelengths. In this work, we clarify the reason behind the nonadiabaticity and provide the solutions for achieving higher degrees of orientation.

Non-linear stress-orientation behavior of flexible chain polymers under fast elongational flow

Closed-form analytical formulas are proposed for non-linear stress-orientation relation valid in the entire range of tensile stresses, intermediate and high, basing on the inverse Langevin chain statistics. Tensile force and orientation characteristics for single, flexible chain macromolecule are reconsidered in a closed-form Padè approximation of the inverse Langevin function in the entire range of chain extensions, as well as the dynamics of molecular deformation and orientation for systems of chains subjected to uniaxial elongational flow. Average stress and orientation tensors, not collinear in the non-linear range, as well as the tensile stress and axial orientation factor of the chain segments in the system are calculated. For the intermediate tensile stresses, the closed-form formula is derived in the first non-Gaussian term approximation of the inverse Langevin function with the assumption of dominating longitudinal elongation of the chains. The high-stress non-linearity formula is derived with the Padè and Peterlin modulus approximations and aligned chain end-to-end vectors by the flow. Both formulas are validated by exact numerical calculations without the assumptions and influence of the approximations is estimated. Ranges of applicability of the formulas are illustrated and examples of their application are presented.

Natural Abundance Nitrogen-15 NMR in Thermotropic Liquid Crystals With Cyano-Group

Abstract We present natural abundance nitrogen-15 (NAN15) NMR spectroscopy in thermotropic liquid crystals. It is demonstrated that high resolution NAN15 NMR spectra in mesophases can be accurately recorded in non-spinning samples with a high orientational molecular order and strong anisotropic spin interactions. In this technique, due to low demand on radio-frequency decoupling power, standard solution-state probes can be used, which generally provide superior sensitivity and spectroscopic resolution in comparison to solid-state probes. We show that 15N chemical shift anisotropy (CSA) can be used as a sensitive probe of molecular orientational dynamics in liquid crystals. This method is exploited here to measure the orientational molecular order parameter of the nematic 4-pentyl-4′-cyanobiphenyl (5CB). Since the nitrogen spectra are obtained from the molecules constituting the mesophase rather than from probe molecules, the information is direct and the analysis and interpretation is straightforward. Nitrogen CSA of immobilized molecules, required in the analysis, is obtained using a DFT calculation. The approach provided consistent results for the order parameter in the nematic 5CB in the whole temperature range, in good agreement with literature data.

Dynamics of Molecular Orientation Observed Using Angle Resolved Photoemission Spectroscopy during Deposition of Pentacene on Graphite.

A real-time method to observe both the structural and the electronic configuration of an organic molecule during deposition is reported for the model system of pentacene on graphite. Structural phase transition of the thin films as a function of coverage is monitored by using in situ angle resolved photoemission spectroscopy (ARPES) results to observe the change of the electronic configuration at the same time. A photoemission theory that uses independent atomic center approximations is introduced to identify the molecular orientation from the ARPES technique. This study provides a practical insight into interpreting ARPES data regarding dynamic changes of molecular orientation during initial growth of molecules on a well-defined surface.

Fast and slow dynamics and the local structure of liquid and supercooled water next to a hydrophobic amino acid

We study, through molecular dynamics simulations, the structure and orientational dynamics of water next to a blocked hydrophobic amino acid, valine (Val), above and below the freezing point of water. The structure and the orientational dynamics of waters with four water neighbors (4WN) and less than four water neighbors (L4WN) in the Val's coordination sphere are deconvoluted. We find that in spite of the excluded volume effects waters with L4WN have faster librational dynamics than bulk water, reminiscent of water at the liquid-vapor interface, and faster orientational dynamics than waters with 4WN, at every temperature. Furthermore, our results show that the pronounced decrease of the orientational retardation factor below ∼255 K observed experimentally is mostly caused by the acceleration of the orientational dynamics of waters with L4WN, while waters with 4WN exhibit only moderate acceleration. The differences between the hydrogen-bond acceptor switching mechanism in the shell and the bulk are also analyzed, and no evidence of especially slow OH groups neither in the 4WN nor in the L4WN populations is found. Finally, we show that waters with 4WN have higher tetrahedrality than bulk water at every temperature although this difference decreases at both high and low temperatures.

Theory of third-order spectroscopic methods to extract detailed molecular orientational dynamics for planar surfaces and other uniaxial systems.

Functionalized organic monolayers deposited on planar two-dimensional surfaces are important systems for studying ultrafast orientational motions and structures of interfacial molecules. Several studies have successfully observed the orientational relaxation of functionalized monolayers by fluorescence depolarization experiments and recently by polarization-resolved heterodyne detected vibrational transient grating (HDTG) experiments. In this article we provide a model-independent theory to extract orientational correlation functions unique to interfacial molecules and other uniaxial systems based on polarization-resolved resonant third-order spectroscopies, such as pump-probe spectroscopy, HDTG spectroscopy, and fluorescence depolarization experiment. It will be shown (in the small beam-crossing angle limit) that five measurements are necessary to completely characterize the monolayer's motions: I(∥)(t) and I(⊥)(t) with the incident beams normal to the surface, I(∥)(t) and I(⊥)(t) with a non-zero incident angle, and a time averaged linear dichroism measurement. Once these measurements are performed, two orientational correlation functions corresponding to in-plane and out-of-plane motions are obtained. The procedure is applicable not only for monolayers on flat surfaces, but any samples with uniaxial symmetry such as uniaxial liquid crystals and aligned planar bilayers. The theory is valid regardless of the nature of the actual molecular motions on interface. We then apply the general results to wobbling-in-a-cone model, in which molecular motions are restricted to a limited range of angles. Within the context of the model, the cone angle, the tilt of the cone relative to the surface normal, and the orientational diffusion constant can be determined. The results are extended to describe analysis of experiments where the beams are not crossing in the small angle limit.

Field-free molecular orientation by femtosecond dual-color and single-cycle THz fields

We theoretically demonstrate the dynamics of field-free molecular orientation under the radiation of a femtosecond dual-color field and a delayed single-cycle terahertz (THz) field, with CO and LiH as the prototype molecules. The results show that the impulsive Raman processes of dual-color field and the resonant effect of the THz field exhibit higher excitation efficiency in a combined way and give rise to a significant enhancement of orientation degree when the THz field is introduced around the full revival time of molecules. It also shows that the dual-color field has an advantage over the single-color field when they combine with the THz field in creating field-free orientation.

Effect of molecular rotation on enantioseparation

Recently, several laser schemes have been proposed to separate racemic mixtures of enantiomers by splitting a molecular beam into subbeams consisting of molecules of definite chirality [Y. Li, C. Bruder, and C. P. Sun, Phys. Rev. Lett. 99, 130403 (2007); X. Li and M. Shapiro, J. Chem. Phys. 132, 194315 (2010)]. These ideas rely on laser-induced effective gauge potentials in an adiabatic basis which lead to a chirality dependent force on the center-of-mass. However, the effect of molecular rotation has been neglected in these studies. Accounting for the full molecular quantum state we find that the potentials from the adiabatic dressed state approach cannot be recovered once the molecular orientation dynamics is included, even in the rotational ground state. This affects substantially the ability to perform enantioseparation in the above mentioned setups.

Disentangling molecular motions involved in the glass transition of a twist-bend nematic liquid crystal through dielectric studies

Broadband dielectric spectroscopy spanning frequencies from 10(-2) to 1.9 × 10(9) Hz has been used to study the molecular orientational dynamics of the glass-forming liquid crystal 1",7"-bis (4-cyanobiphenyl-4'-yl)heptane (CB7CB) over a wide temperature range of the twist-bend nematic phase. In such a mesophase two different relaxation processes have been observed, as expected theoretically, to contribute to the imaginary part of the complex dielectric permittivity. For measurements on aligned samples, the processes contribute to the dielectric response to different extents depending on the orientation of the alignment axis (parallel or perpendicular) with respect to the probing electric field direction. The low-frequency relaxation mode (denoted by μ(1)) is attributed to a flip-flop motion of the dipolar groups parallel to the director. The high-frequency relaxation mode (denoted by μ(2)) is associated with precessional motions of the dipolar groups about the director. The μ(1)-and μ(2)-modes are predominant in the parallel and perpendicular alignments, respectively. Relaxation times for both modes in the different alignments have been obtained over a wide temperature range down to near the glass transition temperature. Different analytic functions used to characterize the temperature dependence of the relaxation times of the two modes are considered. Among them, the critical-like description via the dynamic scaling model seems to give not only quite good numerical fittings, but also provides a consistent physical picture of the orientational dynamics on approaching the glass transition.

Real-Time Measurement of Molecular Orientational Randomization Dynamics during Annealing Treatments by In-Situ Ellipsometry

The molecular orientational randomization dynamics of organic thin films during annealing were measured by real-time in situ ellipsometry. The spirofluorene derivatives used in this work formed amo...