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Typical path integral Monte Carlo approaches use the primitive approximation to compute the probability density for a given path. In this work, we develop the pair discrete variable representation (pair-DVR) approach to study molecular rotations. The pair propagator, which was initially introduced to study superfluidity in condensed helium, is naturally well-suited for systems interacting with a pairwise potential. Consequently, paths sampled using the pair action tend to be closer to the exact paths (compared to primitive Trotter paths) for such systems leading to convergence with less imaginary time steps. Our approach relies on using the pair factorization approach in conjunction with a discretized path integral ground state paradigm to study a chain of planar rotors interacting with a pairwise dipole interaction. We first use the Wigner–Kirkwood density expansion to analyze the asymptotics of the pair propagator in imaginary time. Then, we exhibit the utility of the pair factorization scheme via convergence studies comparing the pair and primitive propagators. Finally, we compute energetic and structural properties of this system including the correlation function and Binder ratio as functions of the coupling strength to examine the behavior of the pair-DVR method near criticality. The density matrix renormalization group results are used for benchmarking throughout. [ABSTRACT FROM AUTHOR]

The reaction coefficient for hydrogen/deuterium (H/D) exchange and the diffusion of hydrated excess protons within amorphous solid water (ASW) are characterized as a function of temperature. For these experiments, water films are deposited on a Pt(111) substrate at 108 K, and reactions with pre-adsorbed hydrogen atoms produce hydrated protons. Upon heating, protons diffuse within the water, and H/D exchange occurs when they encounter D2O probe molecules deposited in the films. The time-dependent concentration of D2O is monitored with infrared spectroscopy, and it indicates the protons diffusion from the substrate and establish an equilibrium distribution prior to significant H/D exchange for temperatures 114 K ≤ T ≤ 134 K. By controlling the distance between the D2O molecules and the substrate, we probe the distribution of protons within the film. It decays as x−2 for the examined range of x (12–52 nm) due to the electric field that develops between the diffusing protons and their image charges in the metal substrate. This agrees with the theoretical distance scaling for the equilibrated proton concentration in a dielectric near a metal boundary. From the proton concentration and the measured D2O decay rate, a lower bound for the proton diffusion coefficient ranging from 10−20 m2/s at 114 K to 10−18 m2/s at 134 K is estimated. The diffusion coefficient has an activation energy of 0.40 eV, which is comparable to energies reported for molecular translations and rotations of H2O, suggesting they may play a critical role in the proton diffusion mechanism within ASW. [ABSTRACT FROM AUTHOR]

We demonstrate that working with a correct phase-space electronic Hamiltonian captures electronic inertial effects. In particular, we show that phase space surface hopping dynamics do not suffer (at least to very high order) from non-physical non-adiabatic transitions between electronic eigenstates during the course of pure nuclear translational and rotational motion. This work opens up many new avenues for quantitatively investigating complex phenomena, including angular momentum transfer between chiral phonons and electrons as well as chiral-induced spin selectivity effects. [ABSTRACT FROM AUTHOR]

We recorded and analyzed the microwave spectra of 2,5-dimethylanisole using a pulsed molecular jet Fourier transform microwave spectrometer and the newly developed Passage And Resonant-Impulse Synergy spectrometer across a frequency range of 2–26.5 GHz with support from quantum chemical calculations. Only one conformer was predicted and observed, where the methoxy group and its adjacent methyl group adopt anti-positions. The two methyl groups, located at the ortho- and meta-positions of the anisole ring, exhibit internal rotation, resulting in quintet splitting of all rotational transitions. The low torsional barrier of the m-methyl group, amounting to 65.723 611(84) cm−1, combined with the intermediate barrier of 451.664(19) cm−1 for the o-methyl group, presented challenges in the spectral analysis. Using the XIAM and BELGI-Cs-2Tops programs, we successfully fitted 460 torsional intrastate rotational transitions, allowing for precise determination of molecular parameters and internal rotation characteristics. The torsional barriers are compared to those in the related isomers 2,3-, 2,4-, and 3,4-dimethylanisole as well as other o- and m-substituted toluene derivatives. [ABSTRACT FROM AUTHOR]

Unlike with the energy, which is a scalar property, machine learning (ML) prediction of vector or tensor properties poses the additional challenge of achieving proper invariance (covariance) with respect to molecular rotation. For the energy gradients needed in molecular dynamics (MD), this symmetry is automatically fulfilled when taking analytic derivative of the energy, which is a scalar invariant (using properly invariant molecular descriptors). However, if the properties cannot be obtained by differentiation, other appropriate methods should be applied to retain the covariance. Several approaches have been suggested to properly treat this issue. For nonadiabatic couplings and polarizabilities, for example, it was possible to construct virtual quantities from which the above tensorial properties are obtained by differentiation and thus guarantee the covariance. Another possible solution is to build the rotational equivariance into the design of a neural network employed in the model. Here, we propose a simpler alternative technique, which does not require construction of auxiliary properties or application of special equivariant ML techniques. We suggest a three-step approach, using the molecular tensor of inertia. In the first step, the molecule is rotated using the eigenvectors of this tensor to its principal axes. In the second step, the ML procedure predicts the vector property relative to this orientation, based on a training set where all vector properties were in this same coordinate system. As the third step, it remains to transform the ML estimate of the vector property back to the original orientation. This rotate–predict–rotate (RPR) procedure should thus guarantee proper covariance of a vector property and is trivially extensible also to tensors such as polarizability. The RPR procedure has an advantage that the accurate models can be trained very fast for thousands of molecular configurations, which might be beneficial where many training sets are required (e.g., in active learning). We have implemented the RPR technique, using the MLatom and Newton-X programs for ML and MD, and performed its assessment on the dipole moment along MD trajectories of 1,2-dichloroethane. [ABSTRACT FROM AUTHOR]

The movements of molecules at interfaces and surfaces are restricted by their asymmetric environments, leading to anisotropic orientational motions. In this work, in-plane orientational motions of the –C=O and –CF3 groups of coumarin 153 (C153) at the air/water interface were measured using time-resolved (TR) vibrational sum frequency generation (SFG). The in-plane orientational time constants of the –C=O and –CF3 groups of C153 are found to be 41.5 ± 8.2 and 36.0 ± 4.5 ps. These values are over five-times faster than that of 198 ± 15 ps for the permanent dipole of the whole C153 molecule at the interface, which may indicate that the two groups experience different interfacial friction in the plane. These differences could also be the result of the permanent dipole of C153 being almost five times those of the –C=O and –CF3 groups. The difference in orientational motions reveals the microscopic heterogeneous environment that molecules experience at the interface. While the interfacial dynamics of the two functional groups are similar, our TR-SFG experiments allowed the quantification of the in-plane dynamics of individual functional groups for the first time. Our experimental findings about the interfacial molecular motion have implications for molecular rotations, energy transfer, and charge transfer at material interfaces, photocatalysis interfaces, and biological cell/membrane aqueous interfaces. [ABSTRACT FROM AUTHOR]

For floppy molecules showing internal rotations and/or large amplitude motions, curvilinear internal coordinates are known to be superior to rectilinear normal coordinates within vibrational structure calculations. Due to the myriad definitions of internal coordinates, automated and efficient potential energy surface generators necessitate a high degree of flexibility, supporting the properties arising from these coordinates. Within this work, an approach to deal with these challenges is presented, including key elements, such as the selection of appropriate fit functions, the exploitation of symmetry, the positioning of grid points, or elongation limits for different coordinates. These elements are tested for five definitions of curvilinear coordinates, with three of them being generated in an automated manner. Calculations for semi-rigid molecules, namely H2O, H2CO, CH2F2, and H2CNH, demonstrate the general functionality of the implemented algorithms. Additional calculations for the HOPO molecule highlight the benefits of these curvilinear coordinates for systems with large amplitude motions. This new implementation allowed us to compare the performance of these different coordinate systems with respect to the convergence of the underlying expansion of the potential energy surface and subsequent vibrational configuration interaction calculations. [ABSTRACT FROM AUTHOR]

Molecular rotations influence numerous condensed matter phenomena but are often difficult to isolate in molecular dynamics (MD) simulations. This work presents a rotational/roto-translational constraint algorithm designed for condensed matter simulations. The method is based on the velocity Verlet scheme, ensuring a direct constraint on velocity and simplifying implementation within material simulation software packages. We implemented the algorithm in a customized version of a CP2K package and validated its effectiveness through MD simulations of molecule and crystal. The results demonstrate successful selective constraint of rotational and roto-translational motions, enabling stable long-term simulations. This capability opens avenues for studying rotation-related phenomena (e.g., paddle-wheel mechanism in solid-state electrolytes) and constrained sampling. [ABSTRACT FROM AUTHOR]

The isomerization of azobenzo-13-crown ether can be expected to be hindered due to the polyoxyethylene linkage connecting the 2,2′-positions of azobenzene. The mixed reference spin-flip time-dependent density functional theory results reveal that the planar and rotational minima of the first photo-excited singlet state (S1) of the trans-isomer pass through a barrier (2.5–5.0 kcal/mol) as it goes toward the torsional conical intersection (S0/S1) geometry (

The microwave spectrum of 2,4-dimethylpyrrole was investigated using a Fourier-transform microwave spectrometer in a supersonic expansion. Torsional splittings arising from two inequivalent methyl internal rotors in combination with hyperfine splittings due to the nuclear quadrupole coupling of the 14N nucleus were observed. The experiments were accompanied by quantum chemical calculations. A total of 1561 rotational lines were assigned and fitted in global fits using the programs XIAM and BELGI-Cs-2Tops-hyperfine, both achieved the measurement accuracy of 4 kHz. Local separate fits were also performed to verify the correctness of the assignment. Accurate experimental molecular and internal rotation parameters could be deduced and compared to the calculated ones. The barrier to internal rotation of the 2-methyl rotor was determined to be 277.830(26) cm−1, essentially the same as the value of about 280 cm−1 found for 2-methylpyrrole but lower than the value of 317 cm−1 found for 2,5-dimethylpyrrole. The torsional barrier value of the 4-methyl rotor is 262.210(27) cm−1, slightly higher than the value of 246 cm−1 found for 3-methylpyrrole. Benchmarking the rotational constants for 2,4- and 2,5-dimethylpyrrole revealed that the MP2/6-31G(d,p) level could be helpful to guide the assignment of microwave spectra of pyrrole derivatives. [ABSTRACT FROM AUTHOR]

In this work, the ultrafast intramolecular rotation behavior of 1,1,2,3,4,5-hexaphenylsilole has been investigated in several solutions with different viscosities using femtosecond transient absorption spectroscopy combined with density functional theory and time-dependent density functional theory calculations. It is demonstrated that the nonradiative process, which competes with radiative decay, involves two main stages, namely the restricted intramolecular rotation and internal conversion processes. The intramolecular rotation depends on viscosity and presents a significant restriction. The restricted rotational rate is determined to be dozens of picoseconds. The following nonradiative process is strongly dominated by intramolecular rotation. The nonradiative decay rate will decrease with the increase in viscosity, leading to a rise in the radiative probability and photoluminous yield. These results have borne out the mechanism of ultrafast restricted intramolecular rotation of aggregation induced emission and provided a detailed photophysical picture of nonradiative processes. [ABSTRACT FROM AUTHOR]

We investigated the rotational spectrum of 2,5-dimethylfluorobenzene containing coupled large amplitude motions of two methyl groups in the frequency range from 2 to 26.5 GHz using a pulsed molecular jet Fourier transform microwave spectrometer. The internal rotation of two inequivalent methyl groups with low torsional barriers (around 16 and 226 cm−1) causes splittings of all rotational transitions into quintets with separations of up to hundreds of MHz between the torsional components. Spectral analysis and modeling of the observed splittings were performed using the programs XIAM and BELGI-Cs-2Tops, whereby the latter achieved measurement accuracy. The methyl internal rotation can be used to examine the electronic and steric environments around the methyl group because they affect the methyl torsional barrier. Electronic properties play a particularly important role in aromatic molecules in the presence of a π-conjugated double bond system. The experimental results were compared with those of quantum chemistry. Benchmark calculations resulted in the conclusion that the B3LYP-D3BJ/6-311++G(d,p) level of theory can be recommended for predicting rotational constants to guide the microwave spectral assignment of dimethylfluorobenzenes in particular and toluene derivatives in general. [ABSTRACT FROM AUTHOR]

Biased and accelerated molecular simulations (BAMS) are widely used tools to observe relevant molecular phenomena occurring on time scales inaccessible to standard molecular dynamics, but evaluation of the physical time scales involved in the processes is not directly possible from them. For this reason, the problem of recovering dynamics from such kinds of simulations is the object of very active research due to the relevant theoretical and practical implications of dynamics on the properties of both natural and synthetic molecular systems. In a recent paper [A. Rapallo et al., J. Comput. Chem. 42, 586–599 (2021)], it has been shown how the coupling of BAMS (which destroys the dynamics but allows to calculate average properties) with Extended Diffusion Theory (EDT) (which requires input appropriate equilibrium averages calculated over the BAMS trajectories) allows to effectively use the Smoluchowski equation to calculate the orientational time correlation function of the head–tail unit vector defined over a peptide in water solution. Orientational relaxation of this vector is the result of the coupling of internal molecular motions with overall molecular rotation, and it was very well described by correlation functions expressed in terms of weighted sums of suitable time-exponentially decaying functions, in agreement with a Brownian diffusive regime. However, situations occur where exponentially decaying functions are no longer appropriate to capture the actual dynamical behavior, which exhibits persistent long time correlations, compatible with the so called subdiffusive regimes. In this paper, a generalization of EDT will be given, exploiting a fractional Smoluchowski equation (FEDT) to capture the non-exponential character observed in the relaxation of intramolecular distances and molecular radius of gyration, whose dynamics depend on internal molecular motions only. The calculation methods, proper to EDT, are adapted to implement the generalization of the theory, and the resulting algorithm confirms FEDT as a tool of practical value in recovering dynamics from BAMS, to be used in general situations, involving both regular and anomalous diffusion regimes. [ABSTRACT FROM AUTHOR]

Donor acceptor (D- π -A) fluorophores containing a donor unit and an acceptor moiety at each end connected by a conjugated linker gained attention in the last decade due to their conjugated system and ease of tunability. These features make them good candidates for various applications such as bioimaging, photovoltaic devices and nonlinear optical materials. Upon excitation of the D- π -A fluorophore, intramolecular charge transfer (ICT) occurs, and it polarizes the molecule resulting in the 'push–pull' system. The emission wavelengths of fluorophores can be altered from UV-vis to NIR region by modifying the donor unit, acceptor moiety and the π linker between them. The NIR emitting fluorophores with restricted molecular rotations are used in aggregation-induced emission (AIE). D- π -A fluorophores with carboxylic acid and cyano groups are preferred in photovoltaic applications, and fluorophores with large surface area are used for two photon absorbing applications. Herein, we report the synthesis, optical properties, and applications of various D- π -A fluorophores in UV-vis and NIR region. [ABSTRACT FROM AUTHOR]

The rotational spectrum of 2 ′ -hydroxyacetophenone has been recorded and assigned for the first time using a Stark-modulated free-jet absorption millimeter-wave (FJ-AMMW) spectrometer in the 59.6–74.5 GHz frequency range. The most stable conformer has been detected and assigned: A = 2277.076(11), B = 1212.113(5) and C = 795.278(5) MHz. It is characterized by a C s symmetry where a strong hydrogen bond between the acetyl oxygen atom and the hydroxyl atom takes place. The transition lines show a fine structure due to the internal rotation of the methyl group, which allowed the determination of a V 3 = 565.1(5) cm − 1 barrier. The corresponding tunneling splittings have been estimated to be 51 MHz. Calculations at the B3LYP-D3(BJ)/Def2-TZVP level underestimate the height of the barrier by about 156 cm − 1 . This value decreases to 25 cm − 1 with MP2/aug-cc-pVTZ. [ABSTRACT FROM AUTHOR]

Organic emitters that exhibit room‐temperature phosphorescence (RTP) in neat films have application potential for optoelectronic devices, bio‐imaging, and sensing. Due to molecular vibrations or rotations, the majority of triplet excitons recombine rapidly via non‐radiative processes in purely organic emitters, making it challenging to observe RTP in amorphous films. Here, a chemical strategy to enhance RTP in amorphous neat films is reported, by utilizing through‐space charge‐transfer (TSCT) effect induced by intramolecular steric hindrance. The donor and acceptor groups interact via spatial orbital overlaps, while molecular motions are suppressed simultaneously. As a result, triplets generated under photo‐excitation are stabilized in amorphous films, contributing to phosphorescence even at room temperature. The solvatochromic effect on the steady‐state and transient photoluminescence reveals the charge‐transfer feature of involved excited states, while the TSCT effect is further experimentally resolved by femtosecond transient absorption spectroscopy. The designed luminescent materials with pronounced TSCT effect show RTP in amorphous films, with lifetimes up to ≈40 ms, comparable to that in a rigid polymer host. Photoluminescence afterglow longer than 3 s is observed in neat films at room temperature. Therefore, it is demonstrated that utilizing intramolecular steric hindrance to stabilize long‐lived triplets leads to phosphorescence in amorphous films at room temperature. [ABSTRACT FROM AUTHOR]

Job rotation is one of the employee development activities that aims to improve and maintain employee performance. Implementation of job rotation policies in the public sector in Indonesia experiences various challenges, including bureaucratic characteristics that prioritize compliance so that job rotations are associated as punishment and political factors that cause job rotations to be exploited by certain parties for their interests. Based on the phenomenon, this exploratory research seeks to explore the perspective of civil servants (PNS) in interpreting the job rotation policy. The findings in this research illustrate that job rotation policy is a dispersion that produces various spectrums. Job rotation has a pliable nature and paradoxical benefits indicate that the job rotation policy has not been implemented consistently across multiple government agencies. The five main perspectives in this research provide an overview of the contradictory perspectives of civil servants. Some civil servants think that job rotations have a positive impact, while others think otherwise. These contradictions show the richness of information and a wide variety of answers and show that job rotation policies are pliable and have paradoxical benefits. [ABSTRACT FROM AUTHOR]

By means of massive (more than 1.2 · 106 molecules) molecular dynamics simulations at 300 K we have disentangled self- and cross-dipolar contributions to the dielectric relaxation of liquid water that cannot be experimentally resolved. We have demonstrated that cross dipolar correlations are of paramount importance. They amount for almost a 60% of the total dielectric amplitude. The corresponding relaxation function is a one-step Debye-like function with a characteristic time, τcross, of the order of the phenomenological Debye time, τD. In contrast, the relaxation function corresponding to the self-contribution is rather complex and contains a fast decay related to dipolar librations and a second relaxation step that can be well described by two exponentials: a low-amplitude fast process (τ0 = 0.31 ps) and a main slow process (τself = 5.4 ps) that fully randomizes the dipolar orientation. In addition to dipolar relaxation functions, we have also calculated scattering-like magnitudes characterizing translation and rotation of water molecules. Although these processes can be considered as "jump" processes in the short time range, at the time scale of about τD–τcross, at which the cross-dipolar correlations decay to zero, the observed behavior cannot be distinguished from that corresponding to uncoupled Brownian translational and rotational diffusion. We propose that this is the reason why the Debye model, which does not consider intermolecular dipolar interactions, seems to work at time t ≳ τD. [ABSTRACT FROM AUTHOR]

We describe a novel ultrahigh vacuum state-to-state molecule/surface scattering apparatus with quantum state preparation of the incident molecular beam and angle-resolved quantum state detection of the scattered molecules. State-resolved detection is accomplished using a tunable mid-infrared laser source combined with a cryogenic bolometer detector and is applicable to any molecule with an infrared-active vibrational transition. Results on rotationally inelastic scattering of CH4 methane from a Ni(111) surface and NiO(111)/Ni(111) oxide film, obtained by the new apparatus, are presented. Molecules scattering from the oxidized surface, compared to those scattering from the bare nickel surface, are more highly excited rotationally and scatter into a broader distribution of angles. The internal alignment of molecular rotation is in addition found to be stronger in molecules scattering from the bare surface. Furthermore, the maxima of the state-resolved angular distributions shift toward and away from surface normal with increasing rotational quantum number J for the oxidized and bare surface, respectively. Finally, the rotational state populations produced in scattering from the oxidized surface are well-described by a Boltzmann distribution, while those produced in scattering from the bare surface exhibit large deviations from their best-fit Boltzmann distributions. These results point toward a marked enhancement in molecule–surface collisional energy exchange induced by oxidation of the nickel surface. [ABSTRACT FROM AUTHOR]

In 3/2‐systems, such as the acetate anion H3CαC′OO−, an sp3 center and an sp2 center are connected by a covalent bond. The interaction of threefold and twofold symmetry results in the pyramidalization of the sp2 center during rotation about bond Esp3−Esp2. Rotation angles ψ=0°, ±60°, ±120°, and ±180° account for conformations with a symmetry plane containing the planar sp2 center CαC′OO. However, in all conformations with rotation angles ψ≠0°, ±60°, ±120°, and ±180° this symmetry plane is lost and pyramidalization must occur with maxima at rotation angles ψ=±30°, ±90°, and ±150°, because the two sides of the sp2 center CαC′OO are different. Inevitably, this leads to a pyramidalization/rotation profile θ/ψ with three maxima, three minima, and six zero‐crossings. Thus, myriads of 3/2‐compounds pyramidalize their sp2 centers each moment to the order of about 2° in a coupled pyramidalization/rotation molecular motion independent of energy. [ABSTRACT FROM AUTHOR]

Objective Methods Results Conclusions The aim of this work was to investigate the solubility and co‐solubilization of fragrance raw materials (FRMs) in sodium dodecyl sulfate (SDS) and polysorbate 20 (P20) surfactant micellar systems, which can advance our knowledge of multi‐solute micellar solubilization and fragrance olfactory performance from product matrices containing the surfactants.The transfer of individual FRMs and binary FRM mixtures into micellar phases was quantified by UV–VIS differential spectroscopy and evaluated in terms of the standard Gibbs free energy change and micelle‐water partition coefficient. Co‐solubilization effects were further evaluated by the deviation ratio.Anionic SDS was found overall to be a more efficient solubilizer than nonionic P20. On an individual basis, micellar solubilization generally increased with solute lipophilicity but was additionally impacted by solute rigidity and steric effects. Micellar solubilization was favoured for more rigid structures and less favoured for FRMs that exhibited larger molecular rotation and steric hindrance. For multi‐solute systems, three co‐solubilization effects were observed: (i) inhibitive effect in which micellar partitioning of both solutes decreased, (ii) an inverse effect where partitioning of one solute increased while the other decreased and (iii) synergistic effect in which partitioning of both solutes increased. During co‐solubilization in P20 micelles, many FRMs competed for solubilization between the polyoxyethylene chains in the outer layer of the micelle, thereby resulting in an inhibitory effect for both solutes. Co‐solubilization of FRM binary mixtures in SDS micelles often resulted in a synergistic increase in micellar solubility, possibly due to micellar swelling, thereby facilitating partitioning of additional solutes into the micelle. An inverse effect in which the micellar solubility of one solute increased, while the other decreased was observed in both surfactant systems with varying degrees of partitioning depending on the composition of the FRM mixture.The results of this study provide valuable insights into the impact of FRM composition on multi‐solute partitioning behaviour and the impact of surfactant type on co‐solubilization in micellar solutions. [ABSTRACT FROM AUTHOR]

Context: We perform density functional theory calculations to study the dependence of the structural and electronic properties of the amino acid sarcosine crystal structure on hydrostatic pressure application. The results are analyzed and compared with the available experimental data. Our findings indicate that the crystal structure and properties of sarcosine calculated using the Grimme dispersion-corrected PBE functional (PBE-D3) best agree with the available experimental results under hydrostatic pressure of up to 3.7 GPa. Critical structural rearrangements, such as unit cell compression, head-to-tail compression, and molecular rotations, are investigated and elucidated in the context of experimental findings. Band gap energy tuning and density of state shifts indicative of band dispersion are presented concerning the structural changes arising from the elevated pressure. The calculated properties indicate that sarcosine holds great promise for application in electronic devices that involve pressure-induced structural changes. Methods: Three widely used generalized gradient approximation functionals—PBE, PBEsol, and revPBE—are employed with Grimme's D3 dispersion correction. The non-local van der Waals density functional vdW-DF is also evaluated. The calculations are performed using the projector-augmented wave method in the Quantum Espresso software suite. The geometry optimization results are visualized using VMD. The Multiwfn and NCIPlot programs are used for wavefunction and intermolecular interaction analyses. [ABSTRACT FROM AUTHOR]

A designed anthracene‐based monomer for topochemical Diels–Alder cycloaddition polymerization crystallized with head‐to‐tail arrangement of molecules, as revealed by single‐crystal X‐ray diffraction (SCXRD) analysis. The diene and dienophile units of adjacent monomer molecules are aligned at an average distance of 4.6 Å, suggesting a favorable crystalline arrangement for their intermolecular Diels–Alder cycloaddition reaction to form a linear polymer. Surprisingly, heating the monomer crystals at a temperature above 125 °C resulted in the formation of intramolecular Diels–Alder cycloadduct, which could be characterized by various spectroscopy and SCXRD analysis. Various time‐dependent studies such as NMR, PXRD, and DSC, studies established that the reaction followed topochemical pathway. Schmidt's topochemical postulates are generally used to predict the topochemical reactivity and product, by analyzing the crystal structure of the reactant. Though the crystal arrangement predicted polymerization, upon heating, the molecule avoided this pathway by undergoing a large rotation to form an intramolecular cycloadduct. Theoretical calculations supported the feasibility of the rotation, exploiting the flexibility of the molecule and voids present. These findings caution that the reliance on Schmidt's criteria for topochemical reactions may sometimes be misleading, especially in heat‐induced reactions. [ABSTRACT FROM AUTHOR]

The intensity and handedness of circularly polarized luminescence (CPL) were successfully controlled by dynamic molecular motion in solutions. Bis(boron difluoride) complexes with chiral salen ligands were synthesized and their photophysical properties were investigated. Although these complexes showed rapid molecular rotation about the C−N bond axis in solution at room temperature, two conformers assigned as atropisomers were observed in the NMR spectra at low temperature. Furthermore, the equilibrium of these atropisomers was found to change depending on the external environment, such as the solvent and temperature, allowing precise control of the intensity and handedness of CPL without luminescence color shifts. Theoretical calculations based on density functional theory (DFT) revealed that intramolecular chiral exciton coupling is the key to changes in CPL properties. [ABSTRACT FROM AUTHOR]

Aggregation-induced emission (AIE) is an interesting luminescence phenomenon. This process describes how unity in the molecular world can produce bright emissions (luminescence). Chemists have adopted this technique to design various luminescent materials to develop efficient diagnostics and therapeutics. In this article, a concise description of AIE and its development is documented. The application of AIE is significant in the field of materials and biology. In the last part of the article, a brief description of various uses is presented. [ABSTRACT FROM AUTHOR]

Molecular gearing systems are technomimetic nanoscale analogues to complex geared machinery in the macroscopic world. They are defined as systems incorporating intermeshed movable parts which perform correlated rotational motions by mechanical engagement. Only recently, new methods to actively drive molecular gearing motions instead of relying on passive thermal activation have been developed. Further progress in this endeavor will pave the way for unidirectional molecular gearing devices with a distinct type of molecular machine awaiting its realization. Within this work an essential step towards this goal is achieved by evidencing directional biases for the light‐induced rotations in our molecular photogear system. Using a custom‐designed LED‐coupled chiral cryo‐HPLC setup for the in situ irradiation of enantiomeric analytes, an intrinsic selectivity for clockwise or counterclockwise rotations was elucidated experimentally. Significant directional biases in the photogearing processes and light‐induced single bond rotations (SBRs) are observed for our photogear with directional preferences of up to 4.8 : 1. Harnessing these effects will allow to rationally design and construct a fully directional molecular gearing motor in the future. [ABSTRACT FROM AUTHOR]

Samples of propyne trapped in solid parahydrogen show multiple peak structures in their infrared spectra. These structures are attributed to molecules in two distinct kinds of matrix sites. The most intense lines are assigned to propyne molecules executing a slightly hindered methyl rotation, as was extensively studied in our earlier publication from our two groups, and the other set of peaks to propyne trapped in a secondary site where the methyl rotation is quenched and replaced by methyl torsion within the matrix site. The assignment of the various rovibrational transitions is made possible by the observation of nuclear spin conversion (NSC) within the methyl group at long timescales. The NSC rate depends on the site and is much slower in the sites where the methyl rotation is quenched. [ABSTRACT FROM AUTHOR]

Neutron time‐of‐flight transmission spectra of mosaic crystals contain Bragg dips, i.e., minima at wavelengths corresponding to diffraction reflections. The positions of the dips are used for investigating crystal lattices. By rotating the sample around a fixed axis and recording a spectrum at each rotation step, the intensity of the transmitted beam is obtained as a function of the rotation angle and wavelength. The questions addressed in this article concern the determination of lattice parameters and orientations of centrosymmetric crystals from such data. It is shown that if the axis of sample rotation is inclined to the beam direction, the reflection positions unambiguously determine reciprocal‐lattice vectors, which is not the case when the axis is perpendicular to the beam. Having a set of such vectors, one can compute the crystal orientation or lattice parameters using existing indexing software. The considerations are applicable to arbitrary Laue symmetry. The work contributes to the automation of the analysis of diffraction data obtained in the neutron imaging mode. [ABSTRACT FROM AUTHOR]

Electronic structure calculations of atoms and molecules are considered to be a promising application for quantum computers. Two key algorithms, the quantum phase estimation (QPE) and the variational quantum eigensolver (VQE), have been extensively studied. The condition that the energy of a dimer consisting of two monomers separated by a large distance should be equal to twice the energy of a monomer, known as size consistency, is essential in quantum chemical calculations. Recently, we reported that the size consistency condition can be violated by Trotterization in the unitary coupled cluster singles and doubles ansatz in the VQE when employing molecular orbitals delocalized to the dimer [Sugisaki et al., J. Comput. Chem. 45, 2204 (2024)]. It is well known that the full configuration interaction (full-CI) energy is invariant to arbitrary rotations of molecular orbitals, and therefore, the QPE-based full-CI should theoretically satisfy the size consistency. However, Trotterization of the time evolution operator can break the size consistency conditions. In this work, we investigated whether size consistency can be maintained with Trotterization of the time evolution operator in QPE-based full-CI calculations. Our numerical simulations revealed that size consistency in the QPE-based full-CI is not automatically violated by using molecular orbitals delocalized to the dimer, but employing an appropriate Trotter decomposition condition is crucial to maintain size consistency. We also report on the acceleration of QPE simulations through the sequential addition of ancillary qubits. [ABSTRACT FROM AUTHOR]

Within chemistry education, methods for effectively teaching students the three-dimensional spatial arrangements of matter at the molecular level remains a topical issue. As a form of geometric problem solving, it requires learners to apply mental rotation abilities as an evolved visuospatial skill to obtain subject-specific content knowledge. Recent research into the use of Cognitive Load Theory (CLT) as a framework for instructional design in conjunction with augmented reality (AR) technology as a learning tool has begun to show promise in reducing unnecessary cognitive activity to improve learning. Yet, broader conclusions remain inconclusive, especially within the context of a learner's mental rotation abilities. This study investigated the relationship between these factors by collecting data using a 2 × 3 experimental design that divided a sample of Year 10 students (n = 42) into two groups. The intervention group (n = 24) used mobile devices utilising AR technology with instructional 3D molecular geometry content featuring design principles based on CLT to encourage hand movements to rotate three-dimensional molecular structures. The non-AR-based control group (n = 18) was taught using traditional methods. Analysis of the data revealed participants using AR technology that featured CLT design principles experienced less cognitive load and improved achievement in post-testing compared to those taught using traditional methods, suggesting under certain conditions, the use of hand movement applied to AR design material improves learning. [ABSTRACT FROM AUTHOR]

We propose a Markovian quantum model for the time dependence of the pressure-induced decoherence of rotational wave packets of gas-phase molecules beyond the secular approximation. It is based on a collisional relaxation matrix constructed using the energy-corrected sudden approximation, which improves the previously proposed infinite order sudden one by taking the molecule rotation during collisions into account. The model is tested by comparisons with time-domain measurements of the pressure-induced decays of molecular-axis alignment features (revivals and echoes) for HCl and CO2 gases, pure and diluted in He. For the Markovian systems HCl–He and CO2–He, the comparisons between computed and measured data demonstrate the robustness of our approach, even when the secular approximation largely breaks down. In contrast, significant differences are obtained in the cases of pure HCl and CO2, for which the model underestimates the decay rate of the alignment at short times. This result is attributed to the non-Markovianity of HCl–HCl and CO2–CO2 interactions and the important contribution of those collisions that are ongoing at the time when the system is excited by the aligning laser pulse. [ABSTRACT FROM AUTHOR]

We report a molecular dynamics study of the heterogeneous crystallization of high-pressure glassy water using (plastic) ice VII as a substrate. We focus on the thermodynamic conditions P ∈ [6–8] GPa and T ∈ [100–500] K, at which (plastic) ice VII and glassy water are supposed to coexist in several (exo)planets and icy moons. We find that (plastic) ice VII undergoes a martensitic phase transition to a (plastic) fcc crystal. Depending on the molecular rotational lifetime τ, we identify three rotational regimes: for τ > 20 ps, crystallization does not occur; for τ ∼ 15 ps, we observe a very sluggish crystallization and the formation of a considerable amount of icosahedral environments trapped in a highly defective crystal or in the residual glassy matrix; and for τ < 10 ps, crystallization takes place smoothly, resulting in an almost defect-free plastic fcc solid. The presence of icosahedral environments at intermediate τ is of particular interest as it shows that such a geometry, otherwise ephemeral at lower pressures, is, indeed, present in water. We justify the presence of icosahedral structures based on geometrical arguments. Our results represent the first study of heterogeneous crystallization occurring at thermodynamic conditions of relevance for planetary science and unveil the role of molecular rotations in achieving it. Our findings (i) show that the stability of plastic ice VII, widely reported in the literature, should be reconsidered in favor of plastic fcc, (ii) provide a rationale for the role of molecular rotations in achieving heterogeneous crystallization, and (iii) represent the first evidence of long-living icosahedral structures in water. Therefore, our work pushes forward our understanding of the properties of water. [ABSTRACT FROM AUTHOR]

An AG-group is an algebraic structure that satisfies the left invertive law and includes its left identity and inverse elements. This framework is naturally suited for representing and manipulating various real-life applications in civil engineering, information engineering, artificial intelligence, and more. In this paper, we present the structural application of AG-groups in data encryption and in the rotational transformation of water molecules. Additionally, numerous authors have explored fuzzy set theory over AG-group systems, yielding many valuable results. Spherical fuzzy set theory, an extension of fuzzy set theory, allows for the representation of uncertainty in decision-making, where there may be multiple possible choices or uncertainty about the degree of membership of an element in a set. However, no prior work has combined spherical fuzzy set theory with AG-groups, which motivates our study. In this paper, we apply spherical fuzzy set theory to AG-groups and introduce the concept of spherical fuzzy AG-subgroupoids. We provide the characterization of spherical fuzzy AG-subgroupoids over AG-groupoids and examine their related properties. As an application of spherical fuzzy sets over AG-groups, we develop the concept of normal spherical fuzzy groups over AG-groups and investigate their various properties. [ABSTRACT FROM AUTHOR]

Three-dimensional (3D) bubble structure of the Sgr-B molecular-cloud complex is derived by a kinematical analysis of CO-line archival cube data of the Galactic Centre (GC) observed with the Nobeyama 45-m telescope. The line-of-sight depth is estimated by applying the face-on transformation method of radial velocity to the projected distance on the Galactic plane considering the Galactic rotation of the central molecular zone (CMZ). The 3D complex exhibits a conical-horn structure with the Sgr-B2 cloud located in the farthest end on the line of sight at radial velocity |$v_{\rm lsr} \sim 70$|  km s |$^{-1}$|⁠ , and the entire complex composes a lopsided bubble opening toward the Sun at |$v_{\rm lsr}\sim 50$| to 30 km s |$^{-1}$|⁠. The line-of-sight extent of the complex is |$\sim 100$|  pc according to the large velocity extent for several tens of km s |$^{-1}$| from Sgr-B2 to the outskirts. The entire complex exhibits a flattened conical bubble with full sizes |$\sim 40 \ {\rm pc} \times 20 \ {\rm pc} \times 100 \ {\rm pc}$| in the l, b and line-of-sight directions, respectively. Based on the 3D analysis, we propose a formation scenario of the giant molecular bubble structure due to a galactic bow shock, and suggest that the star formation in Sgr-B2 was enhanced by dual-side compression (DSC) of the B2 cloud by the Galactic shock wave from up-stream and expanding H  ii region from the down-stream side of the GC Arm I in Galactic rotation. [ABSTRACT FROM AUTHOR]

In this work, we present simulations of the optical rotation (OR) for five molecular crystals at density functional theory level with periodic boundary conditions (DFT‐PBC). Calculations are compared with experimental measurements and show semi‐quantitative agreement with experimental data for three of the crystals: tartatic acid, benzil, and pentaerythritol. For the other two crystals, aspartic acid and glutamic acid, the calculated data are in qualitative agreement with, but two orders of magnitude smaller than, the experimental data. We provide some arguments that support the theoretical predictions and suggest that the experiments should be revisited. We also find that the position of H centers provided in experimental X‐ray data is not sufficiently reliable for simulating OR, and better results are obtained when H atoms are allowed to relax while keeping heavier elements fixed at the experimental positions. Comparison with molecular cluster calculations with a better functional and a larger basis set indicate that the role of intermolecular interactions (reproduced with the PBC technique) is as or more important than the choice of model chemistry. Despite the current limitations in the level of theory that can be employed, these simulations provide a promising avenue to investigate the effect of intermolecular interactions on this sensitive electronic property of molecules and materials. [ABSTRACT FROM AUTHOR]

The interaction between different types of substituents in dicarbollide ligands and their influence on the stabilization of various rotational conformers (rotamers) of transition metal bis(dicarbollide) complexes [3,3′-M(1,2-C2B9H11)2]− are considered. It has been shown that the formation of intramolecular CH···X hydrogen bonds between dicarbollide ligands is determined by the size of the proton acceptor atom X rather than its electronegativity. Due to the stabilization of rotamers with different dipole moments, intramolecular hydrogen bonds between ligands in transition metal bis(dicarbollide) complexes can have a significant impact on the biological properties of their derivatives. In the presence of external complexing metals, weak intramolecular CH···X hydrogen bonds can be broken to form stronger X—>M donor-acceptor bonds. This process is accompanied by the mutual rotation of dicarbollide ligands and can be used in sensors and molecular switches based on transition metal bis(dicarbollide) complexes. [ABSTRACT FROM AUTHOR]

Stars form in the densest regions of molecular clouds; however, there is no universal understanding of the factors that regulate cloud dynamics and their influence on the gas-to-star conversion. This study considers the impact of Galactic shear on the rotation of giant molecular clouds (GMCs) and its relation to the solenoidal modes of turbulence. We estimate the direction of rotation for a large sample of clouds in the |$\mathrm{^{13}CO}$| / |$\mathrm{C^{18}O}$| (3–2) Heterodyne Inner Milky Way Plane Survey (CHIMPS) and their corresponding sources in a new segmentation of the |$\mathrm{^{12}CO}$| (3–2) High-Resolution Survey. To quantify the strength of shear, we introduce a parameter that describes the shear's ability to disrupt growing density perturbations within the cloud. Although we find no correlation between the direction of cloud rotation, the shear parameter, and the magnitude of the velocity gradient, the solenoidal fraction of the turbulence in the CHIMPS sample is positively correlated with the shear parameter and behaves similarly when plotted over Galactocentric distance. GMCs may thus not be large or long-lived enough to be affected by shear to the point of showing rotational alignment. In theory, Galactic shear can facilitate the rise of solenoidal turbulence and thus contribute to suppressing star formation. These results also suggest that the rotation of clouds is not strictly related to the overall rotation of the disc, but is more likely to be the imprint of Kelvin–Helmholtz instabilities in the colliding flows that formed the clouds. [ABSTRACT FROM AUTHOR]

Macrocyclic conformations play a crucial role in regulating their properties. Our understanding of the determinants to control macrocyclic conformation interconversion is still in its infancy. Here we present a macrocycle, octamethyl cyclo[4](1,3-(4,6)-dimethylbenzene)[4]((4,6-benzene)(1,3-dicarboxylate) (OC-4), that can exist at 298 K as two stable atropisomers with C2v and C4v symmetry denoted as C2v-OC-4 and C4v-OC-4, respectively. Heating induces the efficient stepwise conversion of C2v- to C4v-OC-4 via a Cs-symmetric intermediate (Cs-OC-4). It differs from the typical transition state-mediated processes of simple C–C single bond rotations. Hydrolysis and further esterification with a countercation dependence promote the generation of C2v- and Cs-OC-4 from C4v-OC-4. In contrast to C2v-OC-4, C4v-OC-4 can bind linear guests to form pseudo-rotaxans, or bind C60 or C70 efficiently. The present study highlights the differences in recognition behavior that can result from conformational interconversion, as well as providing insights into the basic parameters that govern coupled molecular rotations. The three-dimensional conformation of macrocycles determine their chemical and recognition properties and the factors that influence the interconversion between macrocyclic forms are poorly understood. Here the authors describe a macrocycle existing as two stable atropisomers and the mechanism behind the thermally-induced transition between them. [ABSTRACT FROM AUTHOR]

Atropisomers hold significant fascination, not only for their prevalence in natural compounds but also for their biological importance and wide‐ranging applications as chiral materials, ligands, and organocatalysts. While biaryl and heterobiaryl atropisomers are commonly studied, the enantioselective synthesis of less abundant heteroatom‐linked non‐biaryl atropisomers presents a formidable challenge in modern organic synthesis. Unlike classical atropisomers, these molecules allow rotation around two bonds, resulting in low barriers to enantiomerization through concerted bond rotations. In recent years the discovery of new configurationally stable rare non‐biaryl scaffolds such as aryl amines, aryl ethers and aryl sulfones as well as innovative methodologies to control their configuration have been disclosed in the literature and constitute the topic of this minireview. [ABSTRACT FROM AUTHOR]

Innovative molecule design strategy holds promise for the development of next‐generation acceptor materials for efficient organic solar cells with low non‐radiative energy loss (ΔEnr). In this study, we designed and prepared three novel acceptors, namely BTP‐Biso, BTP‐Bme and BTP‐B, with sterically structured triisopropylbenzene, trimethylbenzene and benzene as side chains inserted into the shoulder of the central core. The progressively enlarged steric hindrance from BTP‐B to BTP‐Bme and BTP‐Biso induces suppressed intramolecular rotation and altered the molecule packing mode in their aggregation states, leading to significant changes in absorption spectra and energy levels. By regulating the intermolecular π–π interactions, BTP‐Bme possesses relatively reduced non‐radiative recombination rate and extended exciton diffusion lengths. The binary device based on PB2 : BTP‐Bme exhibits an impressive power conversion efficiency (PCE) of 18.5 % with a low ΔEnr of 0.19 eV. Furthermore, the ternary device comprising PB2 : PBDB‐TF : BTP‐Bme achieves an outstanding PCE of 19.3 %. The molecule design strategy in this study proposed new perspectives for developing high‐performance acceptors with low ΔEnr in OSCs. [ABSTRACT FROM AUTHOR]

It is well-known that the Spin-Coupled (SC) description of the cyclopentadienyl anion is problematic. A converged six electrons in six orbitals SC calculation on this anion break the D5h electron density spatial symmetry by approximately localizing two of the six pi singly-occupied orbitals over one carbon. A complete active space valence bond (CASVB) calculation for the same six pi electrons in six orbitals does not break symmetry, yielding five equivalent pi orbitals over the five carbons and one pi orbital with high amplitude along the C5 molecular rotation axis. A Spin-Coupled calculation comprising six electrons in five orbitals, SC(6,5), yields five equivalent non-orthogonal pi orbitals over the carbons with "1.2" (6/5) electron occupancy each. In this paper, these different solutions are contrasted with one generated by the present author in which five spatially different but equivalent configurations of a perfect-pairing symmetry broken solution are put together in a multi-configuration Spin-Coupled calculation of six electrons in 30 orbitals. It is concluded that, in spite of the computational complexity of this calculation, its result is qualitatively more akin to a valence bond-like description of the resonant pi system of the cyclopentadienyl anion. [ABSTRACT FROM AUTHOR]

In this study, the molecular dynamics (MD) method was used to study the tensile deformation of polycrystalline γ-TiAl with complex and random grain orientations. Firstly, the tensile deformation was simulated with different average grain sizes (8.60 nm, 6.18 nm, and 4.50 nm) and strain rates (1 × 108 s−1, 5 × 108 s−1, and 1 × 109 s−1). The results show that the peak stress increases with an increase in tensile strain rate, and the peak stress decreases as the grain size decreases, showing an inverse Hall–Petch effect. Upon observing atomic configuration evolution during tensile deformation, it is found that the grain boundary is seriously distorted, which indicates obvious grain boundary sliding occurring. With a further increase in the loading, some dislocations nucleate at the grain boundaries and propagate towards the interior of the grains along the grain boundaries, which demonstrates that dislocation motion is the primary coordination of the mechanical process of the grain boundaries. The dislocation density near the grain boundaries continues to increase, leading to the generation of micro-cracks and eventually causing material failure. Another interesting phenomenon is that the grains rotate, and the specific rotation angle values of each grain are quantitatively calculated. Grain rotation relaxes the stress concentration near the grain boundaries and plays a toughening role. Consequently, the plastic deformation behaviors of polycrystalline γ-TiAl are achieved through the grain boundary mechanical process, that is, grain boundary sliding and grain rotation. [ABSTRACT FROM AUTHOR]

Many diseases in the human body are related to the overexpression of viscosity and sulfur dioxide. Therefore, it is essential to develop rapid and sensitive fluorescent probes to detect viscosity and sulfur dioxide. In the present work, we developed a dual-response fluorescent probe (ES) for efficient detection of viscosity and sulfur dioxide while targeting mitochondria well. The probe generates intramolecular charge transfer by pushing and pulling the electron–electron system, and the ICT effect is destroyed and the fluorescence quenched upon reaction with sulfite. The rotation of the molecule is inhibited in the high-viscosity system, producing a bright red light. In addition, the probe has good biocompatibility and can be used to detect sulfite in cells, zebrafish and mice, as well as upregulation of viscosity in LPS-induced inflammation models. We expect that the dual response fluorescent probe ES will be able to detect viscosity and sulfite efficiently, providing an effective means of detecting viscosity and sulfite-related diseases. [ABSTRACT FROM AUTHOR]

Developing efficient long‐wavelength thermally activated delayed fluorescence (TADF) emitters is a challenging issue due to inherent limitations of the energy‐gap law. In this contribution, a new molecular design of cyanobenzene‐decorated quinoxaline acceptor, combining two or four cyanobenzene acceptors and a rigid carbazole donor, is successfully utilized to construct long‐wavelength TADF emitters (tCzQx2CN and tCzQx4CN). The two additional cyanobenzene units at the 5‐ and 8‐positions of the quinoxaline acceptor are presumed to interlock the molecular rotations and improve the acceptor strength. Compared with tCzQx2CN, tCzQx4CN exhibits orange‐red emission with a considerable bathochromic shift (>35 nm), as expected. Owing to its enhanced charge transfer and well‐separated highest‐occupied and lowest‐unoccupied molecular orbitals, tCzQx4CN exhibits reduced singlet‐triplet energy splitting and improves reverse intersystem crossing. An organic light–emitting diode (OLED) of tCzQx4CN manifestes bright orange‐red emission (λEL ≈581 nm), a superior external quantum efficiency (EQE) of ≈23.7% (compared with that of tCzQx2CN), and a satisfactory operational lifetime. Furthermore, a tCzQx4CN‐sensitized red‐hyperfluorescent OLED device exhibits excellent performance with an EQE of 16.0% and a CIE(x,y) of (0.62, 0.37). This design would potentially pave the way for constructing red/deep‐red TADF emitters by using a diverse combination of donor/acceptor units. [ABSTRACT FROM AUTHOR]

We propose a new concept for the regularization and discretization of transfer and Koopman operators in dynamical systems. Our approach is based on the entropically regularized optimal transport between two probability measures. In particular, we use optimal transport plans in order to construct a finite-dimensional approximation of some transfer or Koopman operator which can be analyzed computationally. We prove that the spectrum of the discretized operator converges to the one of the regularized original operator, give a detailed analysis of the relation between the discretized and the original peripheral spectrum for a rotation map on the n -torus and provide code for three numerical experiments, including one based on the raw trajectory data of a small biomolecule from which its dominant conformations are recovered. [ABSTRACT FROM AUTHOR]

In recent years, several artificial molecular motors driven and controlled by electric currents have been proposed. Similar to Brownian machines, these systems work by turning random inelastic tunneling events into a directional rotation of the molecule. Despite their importance as the ultimate component of future molecular machines, their modeling has not been sufficiently studied. Here, we develop a dynamical model to describe these systems. We illustrate the validity and usefulness of our model by applying it to a well-known molecular motor, showing that the obtained results are consistent with the available experimental data. Moreover, we demonstrate how to use our model to extract some difficult-to-access microscopic parameters. Finally, we include an analysis of the expected effects of current-induced forces (CIFs). Our analysis suggests that, although nonconservative contributions of the CIFs can be important in some scenarios, they do not seem important in the analyzed case. Despite this, the conservative contributions of CIFs could be strong enough to significantly alter the system's dynamics. [ABSTRACT FROM AUTHOR]

Recently, a large family of at least 14 discotic liquid crystals was discovered that are exceptions to the conventional paradigm that discotic mesogens tend to feature long, flexible tails on their periphery. To understand why these materials are liquid crystals, as well as the structural determinants of discotic phase behavior, we studied a group of closely related small tail-free disk-like molecules, including both mesogenic and non-mesogenic compounds differing only in the position of a single fluorine substituent. The rigidity and structural simplicity of these molecules make them well suited to for study by large, fully all-atom simulations. Using a combination of static and dynamic metrics, we were able to identify several key features of the columnar mesophase and, thereby, conclusively identify a columnar liquid crystalline mesophase present in a subset of our systems. Our simulations feature molecules hopping between columns in the columnar mesophase and distinctive molecular rotations in 60° steps about the columnar axis. The ability to create and characterize columnar mesophases in silico provides a potent tool for untangling the structural determinants of liquid crystalline behavior in these and other tail-free discotic liquid crystals. [ABSTRACT FROM AUTHOR]

Molecular rotations and vibrations have been extensively studied by chemists for decades, both experimentally using spectroscopic methods and theoretically with the help of quantum chemistry. However, the theoretical investigation of molecular rotations and vibrations in strong magnetic fields requires computationally more demanding tools. As such, proper calculations of rotational and vibrational spectra were not feasible up until very recently. In this work, we present rotational and vibrational spectra for two small linear molecules, H2 and LiH, in strong magnetic fields. By treating the nuclei as classical particles, trajectories for rotations and vibrations are simulated from ab initio molecular dynamics. Born–Oppenheimer potential energy surfaces are calculated at the Hartree–Fock and MP2 levels of theory using London atomic orbitals to ensure gauge origin invariance. For the calculation of nuclear trajectories, a highly efficient Tajima propagator is introduced, incorporating the Berry curvature tensor accounting for the screening of nuclear charges. [ABSTRACT FROM AUTHOR]

For decades, it was considered all but impossible to perform Stark spectroscopy on molecules in a liquid solution, because their concomitant orientation to the applied electric field results in overwhelming background signals. A way out was to immobilize the solute molecules by freezing the solvent. While mitigating solute orientation, freezing removes the possibility to study molecules in liquid environments at ambient conditions. Here we demonstrate time-resolved THz Stark spectroscopy, utilizing intense single-cycle terahertz pulses as electric field source. At THz frequencies, solute molecules have no time to orient their dipole moments. Hence, dynamic Stark spectroscopy on the time scales of molecular vibrations or rotations in both non-polar and polar solvents at arbitrary temperatures is now possible. We verify THz Stark spectroscopy for two judiciously selected molecular systems and compare the results to conventional Stark spectroscopy and first principle calculations. Stark spectroscopy of molecules in liquid solutions was once challenging due to orientation effects, solved by freezing but limiting ambient studies. Now, THz Stark spectroscopy with intense terahertz pulses enables dynamic analysis of molecules in both non-polar and polar solvents at any temperature, advancing conventional methods. [ABSTRACT FROM AUTHOR]