Chris Welch

Disentangling the relative contribution of the intra - and inter -molecular dipolar associations on the static dielectric properties of liquid crystalline dimer–monomer mixtures.

In sulfur containing liquid crystal dimers we find that at the transition to the N _TB phase the positional correlation length drops. The nanoscale periodicity was also observed in the upper range of a smectic phase that forms below the N _TB state.

Fourier-transform infrared polarized spectroscopy was employed, to obtain the three components of the infrared absorbance for a series of bent-shaped dimers containing double fluorinated terphenyl core (DTC5Cn, n = 5, 7, 9, 11). The data were used to calculate both uniaxial and biaxial order parameters, for various molecular groups of dimers. The molecule bend was estimated based on the observed differences between the uniaxial order parameters for the terphenyl core and central hydrocarbon linker. The orientational order, distinctly reverses its monotonic trend of increase to decrease at the transition temperature, from the uniaxial nematic to the twist-bend nematic phase as result of the director tilt in latter/(twist-bend) phase. The molecular biaxiality, which is negligible in the nematic phase, starts increasing on entering the twist-bend nematic phase, following a sin-square relationships with the tilt angle. The local director curvature is found to be controlled by the molecular biaxiality parameter.

The understanding of the relationship between molecular structure and the formation of the nematic twist-bend phase is still at an early stage of development. This is mainly related to molecular geometry, while the correlation between the nematic twist-bend phase and the electronic structure is ambiguous. To explore the electronic effect on properties and stabilization of the nematic twist-bend phase we investigated 2′,3′-difluoro-4,4′′-dipentyl-p-terphenyl dimers (DTC5Cn). We used polarized fourier transform infrared spectroscopy, which can, at least in principle, provide information about the ordering in the twist-bend phase. All dimers show a significant drop in the average value of the transition dipole moment for parallel dipoles at the transition from the nematic to the twist-bend phase, and an increase for perpendicular dipoles, despite remaining unchanged for the monomer. Density functional theory calculations were used to determine the geometric and electronic properties of the hydrogen bonded complexes. We have provided experimental and theoretical evidence of stabilization of the nematic twist-bend phase by arrays of multiple hydrogen bonds (XF⋯HX, X–benzene ring).

Wavefront shaping, which is often achieved using liquid crystal (LC) spatial light modulators, is particularly important for a wide range of applications including laser microfabrication and micromanipulation, microscopy, and quantum optics. In this work, results are presented for the first integrated LC phase modulator that combines a flexoelectro‐optic LC layer (that behaves as a switchable λ/2 waveplate) with a polymerized reactive mesogen layer (which acts as a λ/4 waveplate) and a mirrored substrate that creates a double‐pass geometry. For a flexoelectro‐optic LC layer that exhibits switching angles of ±45° at a voltage of ±85 V a full 2π phase modulation is observed when driven by a 1 kHz waveform. Experimental results are also compared with modeling using Jones calculus of the amplitude and phase variation when the LC and the polymer layer deviate from their desired waveplate conditions. The development and demonstration of an integrated device is particularly significant for applications where size and cost are critical factors such as in LiDAR for the Space and Automotive industries, respectively.

Chirality amplification in mesomorphic gold nanoparticles (NPs) functionalized with chiral ligands and liquid crystal (LC) groups in LC matrices is detected. Attaching LC groups to NPs leads to a significant increase of the helical twisting power.

In this paper, we demonstrate analog phase modulation in a transmissive configuration using the flexoelectro-optic effect in short-pitch chiral nematic liquid crystal (LC) devices. Two different modes are considered, both of which are shown to generate full 2π phase modulation at 1 kHz switching frequency. The first configuration that is considered consists of a half-wave plate that is placed between two flexoelectro-optic LC devices that are subjected to electric fields that are applied in phase. Second, we demonstrate that a similar phase modulation response can be observed by removing the half-wave plate and subjecting the two flexoelectro-optic LC devices to electric fields whereby the polarities are out of phase. Both configurations demonstrated herein are promising for the development of next-generation LC spatial light modulators, particularly when reflective geometries are challenging or impractical.

The quadrupolar splittings of perdeuteriated n-decane dissolved in nematic phases formed by mesogenic dimers of the CBnCB series, for n = 7,9,10,11, are measured throughout the entire temperature range of these phases. These results are reported together with related measurements using the common nematic phase of 5CB as a solvent for n-decane. The data obtained from the ¹³C spectra of the cyanobiphenyl mesogenic units of the monomeric and dimeric solvent molecules yield the order parameter of those units. The information obtained from this set of experiments is used to elucidate the structure of the low temperature (N_X) and the high temperature (N) nematic phases of CBnCB dimers with n = 7,9,11. The polar twisted nematic (N_PT) model is found to provide a consistent description not only of our experimental results but also of NMR measurements previously reported in the literature for these phases. These findings suggest that the high temperature nematic (N) is not a common, locally uniaxial and apolar nematic, but rather a nematic phase consisting of N_PT clusters. The twist-bend (N_TB) model, often identified with the N_X phase, is shown to be inadequate to account even qualitatively for crucial features of the experimental findings. NMR studies of perduteriated n-decane dissolved in mesogenic dimers of the CBnCB series elucidate the structure of the low and high temperature nematic phases of the odd-n dimers.

Many achiral bent molecules and some polymers with such repeat units exhibit a liquid crystal phase transition between a conventional nematic (N), and a second nematic (N_x) with periodically modulated orientation. Theory predicts several possible structures for the N_x phase, some of which are chiral (helical), and others achiral (e.g. zigzag). Experimentally distinguishing which modulation type is present is non-trivial and the structure is often assumed to be helical despite the other possibilities. Here we use circular dichroism (CD) spectroscopy to directly and unambiguously identify chirality in the N_x phase of two different dimer series, “DTC5Cn” and “CBCnCB”, which vary in (CH₂)_n spacer length (n = 5, 7, 9). In doing so we have determined that the modulation type is helical in all samples. The temperature dependence of the CD signal was also investigated, suggesting that the helical structure progressively unwinds on approach to the high temperature N phase.