Correction to "Ligand Chromophore Modification Approach for Predictive Incremental Tuning of Metal-Organic Framework Color".

[This corrects the article DOI: 10.1021/acs.chemmater.3c01603.].

Isotope Effects in the Zundel-Eigen Isomerization of H+(H2O)6.

The isomerization pathway between the energetically low-lying Zundel and Eigen isomers of the protonated water hexamer was investigated using high-level ab initio calculations including a treatment of zero-point corrections. On the basis of these calculations, the Zundel-Eigen isomerization was found to proceed through a stable intermediate isomer, which consists of a four-membered ring with two single acceptor water molecules. The inclusion of vibrational zero-point energy is shown to be important for accurately establishing the relative energies of the three relevant isomers involved in the Zundel-Eigen isomerization. Diffusion Monte Carlo calculations including anharmonic vibrational effects show that all three isomers of H+(H2O)6 and D+(D2O)6 have well-defined structures. The energetic ordering of the three isomers changes upon deuteration. The implications of these results for the vibrational spectra of H+(H2O)6 and D+(D2O)6 are also discussed.

Light control using vertically aligned dichroic dye films for windshield antireflection in automotive displays.

A vertically aligned dichroic dye (VA-Dye) film, whose absorption axis is perpendicular to that of its substrates, was laminated on a display panel in which the absorption axis of the top polarizer was set to 0°. In the vertical viewing angle of the display panel, the absorption axes of the top polarizer and dichroic dye are at right angles to each other, and, so, the light emitted from the display panel can be blocked. In the horizontal viewing angle of the display panel, the absorption axes of the top polarizer and dichroic dye are parallel to each other so that the light emitted from the display panel can be transmitted. Based on these polarization optics, we achieved complete elimination of light emitted in the upward or downward direction of the display panel, while the light emitted to the left and right is transmitted. We also added a designed optical compensation film using a positive biaxial (+B) retarder to the VA-Dye film so that the light emitted in the upward and downward directions of the display panel could be blocked in a wide viewing angle range (not only in the vertical direction, but also in the diagonal direction). The display panel using the VA-Dye film with the +B retarder showed excellent optical performance, such as significantly lower transmittance over a wide viewing angle range in the upward direction and relatively higher transmittance compared to that of a reference panel without the VA-Dye film. In addition, the VA-Dye film can be manufactured with a lower thickness, easier fabrication, and lower cost when compared with other technologies.

A simulation of diffractive liquid crystal smart window for privacy application.

Using a single substrate, we demonstrate a simple two-dimensional (2-D) phase grating cell with an octothorp electrode. Owing to the large spatial phase difference in any direction, the proposed grating cell has a high haze value in the opaque state (76.7%); Moreover, it has the advantages of a one-dimensional (1-D) phase grating cell, such as high fabricability, fast response time, and low operating voltage. Furthermore, the proposed grating cell has a faster response time than the 2-D grating cell (comparable to a 1-D grating cell). All the electro-optic parameters have been calculated using a commercial modeling tool. Consequently, we expect our proposed grating cell to find applications in virtual reality (VR)/augmented reality (AR) systems or window displays with fast response times.

Water Network Shape-Dependence of Local Interactions with the Microhydrated -NO2- and -CO2- Anionic Head Groups by Cold Ion Vibrational Spectroscopy.

We report the structural evolutions of water networks and solvatochromic response of the CH3NO2- radical anion in the OH and CH stretching regions by analysis of the vibrational spectra displayed by cryogenically cooled CH3NO2-·(H2O)n=1-6 clusters. The OH stretching bands evolve with a surprisingly large discontinuity at n = 6, which features the emergence of an intense, strongly red-shifted band along with a weaker feature that appears in the region assigned to a free OH fundamental. Very similar behavior is displayed by the perdeuterated carboxylate clusters, RCO2-·(H2O)n=5-7 (R = CD3CD2), indicating that this behavior is a general feature in the microhydration of the triatomic anionic domain and not associated with CH oscillators. Electronic structure calculations trace this behavior to the formation of a "book" isomer of the water hexamer that adopts a configuration in which one of the water molecules resides in an acceptor-acceptor-donor (AAD) (A = acceptor, D = donor) H-bonding site. Excitation of the bound OH in the AAD site explores the local network topology best suited to stabilize an incipient -XO2H-OH-(H2O)2 intracluster proton-transfer reaction. These systems thus provide particularly clear examples where the network shape controls the potential energy landscape that governs water network-mediated, intracluster proton transfer. The CH stretching bands of the CH3NO2-·(H2O)n=1-6 clusters also exhibit strong solvatochromic shifts, but in this case, they smoothly blue-shift with increasing hydration with no discontinuity at n = 6. This behavior is analyzed in the context of the solute-ion polarizability response and partial charge transfer to the water networks.

Vibrational Signatures of HNO3 Acidity When Complexed with Microhydrated Alkali Metal Ions, M+·(HNO3)(H2O)n=5 (M = Li, K, Na, Rb, Cs), at 20 K.

The speciation of strong acids like HNO3 under conditions of restricted hydration is an important factor in the rates of chemical reactions at the air-water interface. Here, we explore the trade-offs at play when HNO3 is attached to alkali ions (Li+-Cs+) with four water molecules in their primary hydration shells. This is achieved by analyzing the vibrational spectra of the M+·(HNO3)(H2O)5 clusters cooled to about 20 K in a cryogenic photofragmentation mass spectrometer. The local acidity of the acidic OH group is estimated by the extent of the red shift in its stretching frequency when attached to a single water molecule. The persistence of this local structural motif (HNO3-H2O) in all of these alkali metal clusters enables us to determine the competition between the effect of the direct complexation of the acid with the cation, which acts to enhance acidity, and the role of the water network in the first hydration shell around the ions, which acts to counter (screen) the intrinsic effect of the ion. Analysis of the vibrational features associated with the acid molecule, as well as those of the water network, reveals how cooperative interactions in the microhydration regime conspire to effectively offset the intrinsic enhancement of HNO3 acidity afforded by attachment to the smaller cations.

Computational predictions of metal-macrocycle stability constants require accurate treatments of local solvent and pH effects.

Rational design of molecular chelating agents requires a detailed understanding of physicochemical ligand-metal interactions in solvent phase. Computational quantum chemistry methods should be able to provide this, but computational reports have shown poor accuracy when determining absolute binding constants for many chelating molecules. To understand why, we compare and benchmark static- and dynamics-based computational procedures for a range of monovalent and divalent cations binding to a conventional cryptand molecule: 2.2.2-cryptand ([2.2.2]). The benchmarking comparison shows that dynamics simulations using standard OPLS-AA classical potentials can reasonably predict binding constants for monovalent cations, but these procedures fail for divalent cations. We also consider computationally efficient static procedure using Kohn-Sham density functional theory (DFT) and cluster-continuum modeling that accounts for local microsolvation and pH effects. This approach accurately predicts binding energies for monovalent and divalent cations with an average error of 3.2 kcal mol-1 compared to experiment. This static procedure thus should be useful for future molecular screening efforts, and high absolute errors in the literature may be due to inadequate modeling of local solvent and pH effects.

Quantifying Uncertainties in Solvation Procedures for Modeling Aqueous Phase Reaction Mechanisms.

Computational quantum chemistry provides fundamental chemical and physical insights into solvated reaction mechanisms across many areas of chemistry, especially in homogeneous and heterogeneous renewable energy catalysis. Such reactions may depend on explicit interactions with ions and solvent molecules that are nontrivial to characterize. Rigorously modeling explicit solvent effects with molecular dynamics usually brings steep computational costs while the performance of continuum solvent models such as polarizable continuum model (PCM), charge-asymmetric nonlocally determined local-electric (CANDLE), conductor-like screening model for real solvents (COSMO-RS), and effective screening medium method with the reference interaction site model (ESM-RISM) are less well understood for reaction mechanisms. Here, we revisit a fundamental aqueous hydride transfer reaction-carbon dioxide (CO2) reduction by sodium borohydride (NaBH4)-as a test case to evaluate how different solvent models perform in aqueous phase charge migrations that would be relevant to renewable energy catalysis mechanisms. For this system, quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations almost exactly reproduced energy profiles from QM simulations, and the Na+ counterion in the QM/MM simulations plays an insignificant role over ensemble averaged trajectories that describe the reaction pathway. However, solvent models used on static calculations gave much more variability in data depending on whether the system was modeled using explicit solvent shells and/or the counterion. We pinpoint this variability due to unphysical descriptions of charge-separated states in the gas phase (i.e., self-interaction errors), and we show that using more accurate hybrid functionals and/or explicit solvent shells lessens these errors. This work closes with recommended procedures for treating solvation in future computational efforts in studying renewable energy catalysis mechanisms.

Mapping the temperature-dependent and network site-specific onset of spectral diffusion at the surface of a water cluster cage.

We explore the kinetic processes that sustain equilibrium in a microscopic, finite system. This is accomplished by monitoring the spontaneous, time-dependent frequency evolution (the frequency autocorrelation) of a single OH oscillator, embedded in a water cluster held in a temperature-controlled ion trap. The measurements are carried out by applying two-color, infrared-infrared photodissociation mass spectrometry to the D3O+·(HDO)(D2O)19 isotopologue of the "magic number" protonated water cluster, H+·(H2O)21 The OH group can occupy any one of the five spectroscopically distinct sites in the distorted pentagonal dodecahedron cage structure. The OH frequency is observed to evolve over tens of milliseconds in the temperature range (90 to 120 K). Starting at 100 K, large "jumps" are observed between two OH frequencies separated by ∼300 cm-1, indicating migration of the OH group from the bound OH site at 3,350 cm-1 to the free position at 3,686 cm-1 Increasing the temperature to 110 K leads to partial interconversion among many sites. All sites are observed to interconvert at 120 K such that the distribution of the unique OH group among them adopts the form one would expect for a canonical ensemble. The spectral dynamics displayed by the clusters thus offer an unprecedented view into the molecular-level processes that drive spectral diffusion in an extended network of water molecules.

Liquid crystal cell asymmetrically anchored for high transmittance and triggered with a vertical field for fast switching.

The optical performance of an asymmetrically surface-anchored liquid crystal (LC) cell driven with three-terminal electrodes is demonstrated. The transmittance of an asymmetrically anchored cell is considerably higher than that of a symmetrically anchored cell. However, the slow response of an asymmetrically anchored cell makes its practical application difficult. In this work, we demonstrate that the slowest GTG response time from a high to low grey level in an asymmetrically anchored cell can be reduced to less than 0.7 ms by applying a vertical trigger pulse with three-terminal electrodes while maintaining the high transmittance of an asymmetrically anchored cell.

Correlation Analysis between Ocular Surface Parameters with Subjective Symptom Severity in Dry Eye Disease.

PURPOSE: To evaluate the clinical symptoms of patients with dry eyes, based on the ocular surface disease index (OSDI) and analyze the relationship between OSDI and various ocular surface parameters. METHODS: This was a retrospective study that included 45 eyes of 45 dry eye patients who visited the Seoul Nune Eye Hospital from August 2017 to December 2017. The patients were assessed by non-invasive keratography for the first break-up time, lipid layer thickness (LLT), tear osmolarity, tear matrix metalloproteinase-9 immunoassay as well as with the conventional Schirmer I test and fluorescein break-up time. The patient's symptoms were evaluated by the OSDI questionnaires and correlations were analyzed based on the parameters described above. RESULTS: There were significant negative correlations between OSDI and non-invasive keratography for the first break-up time (p = 0.038, r = -0.330), and LLT (p = 0.005, r = -0.426). However, there were no significant correlations between OSDI and fluorescein break-up time, Schirmer I score, and tear osmolarity (p = 0.173, 0.575, and 0.844 respectively). OSDI was not significantly different between matrix metalloproteinase-9 positive and negative groups (p = 0.768). CONCLUSIONS: Non-invasive examinations such as non-invasive keratograph break-up time and interferometry of LLT can be efficient tools for evaluating dry eye symptoms.

Formation of Polymer Walls through the Phase Separation of a Liquid Crystal Mixture Induced by a Spatial Elastic Energy Difference.

We propose a method to form polymer walls without the use of a photomask in a liquid crystal (LC) cell by phase separation of an LC mixture induced by a spatial elastic energy difference. When an in-plane electric field is applied to a vertically aligned cell filled with a mixture of LC and a reactive monomer (RM), a high spatial elastic energy is induced along the direction perpendicular to the interdigitated electrodes. RMs move to the boundaries where the elastic energy is very high and an in-plane component of the applied electric field exists, which results in the phase separation of the LC/RM mixture. We have shown that we can form polymer walls by applying ultraviolet light irradiation to the LC cell. These polymer walls can function as alignment layers. We observed morphological patterns of the polymer structure through polarized optical microscopy, scanning electron microscopy, and atomic force microscopy. The polymer walls formed in an LC cell can affect the orientation of LCs in the lateral direction. Bistable switching of a polymer-walled cell could be achieved by using three-terminal electrodes where both vertical and in-plane electric fields can be applied. Vertical anchoring with the alignment layer on each substrate allows LC molecules to remain vertically aligned after removal of the applied vertical electric field. Furthermore, in-plane anchoring with the formed polymer walls allows the LC molecules to remain homogeneously aligned after removal of the applied in-plane electric field. The proposed method for the formation of polymer structures could be a useful tool to fabricate LC cells for various applications. As a bistable phase-grating device, the diffraction efficiency of a polymer-walled cell was comparable to that of a pure-LC cell. Its operating voltage was 44% lower than that of a pure-LC cell owing to in-plane anchoring provided by the polymer walls. Moreover, it can be operated with very low power because it does not require power to maintain the state. In addition, the total response time of a polymer-walled cell was approximately 68% shorter than that of a pure-LC cell because all switching was forcibly controlled by applying an electric field.

Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air-water interface.

We exploit gas-phase cluster ion techniques to provide insight into the local interactions underlying divalent metal ion-driven changes in the spectra of carboxylic acids at the air-water interface. This information clarifies the experimental findings that the CO stretching bands of long-chain acids appear at very similar energies when the head group is deprotonated by high subphase pH or exposed to relatively high concentrations of Ca2+ metal ions. To this end, we report the evolution of the vibrational spectra of size-selected [Ca2+·RCO2-]+·(H2O) n=0to12 and RCO2-·(H2O) n=0to14 cluster ions toward the features observed at the air-water interface. Surprisingly, not only does stepwise hydration of the RCO2- anion and the [Ca2+·RCO2-]+ contact ion pair yield solvatochromic responses in opposite directions, but in both cases, the responses of the 2 (symmetric and asymmetric stretching) CO bands to hydration are opposite to each other. The result is that both CO bands evolve toward their interfacial asymptotes from opposite directions. Simulations of the [Ca2+·RCO2-]+·(H2O) n clusters indicate that the metal ion remains directly bound to the head group in a contact ion pair motif as the asymmetric CO stretch converges at the interfacial value by n = 12. This establishes that direct metal complexation or deprotonation can account for the interfacial behavior. We discuss these effects in the context of a model that invokes the water network-dependent local electric field along the C-C bond that connects the head group to the hydrocarbon tail as the key microscopic parameter that is correlated with the observed trends.

Independent control of haze and total transmittance with a dye-doped liquid crystal phase-grating device.

This paper presents a dye-doped liquid crystal (LC) phase-grating cell that is switchable between transparent, dark, and opaque states. The device can control haze and transmittance independently. Initially, LC and dye molecules are twist-aligned to make the cell opaque but haze-free due to the absorption of incident light without scattering. Switching to the transparent state could be achieved by applying a vertical electric field, whereas switching to the opaque state could be achieved by applying an in-plane electric field. It exhibited several advantages, such as a low switching voltage (<18 V) and fast response time (<30 ms).

Model potential study of non-valence correlation-bound anions of (C60)n clusters: the role of electric field-induced charge transfer.

A polarization model which accounts for electric field-induced charge transfer between fullerene molecules is introduced. Application of this model to the C60 dimer and trimer shows that intermolecular charge transfer makes a significant contribution to the polarizabilities of these clusters. This polarization model is incorporated into a one-electron Hamiltonian for describing non-valence correlation-bound anions, allowing us to further demonstrate that intermolecular charge transfer also results in increased stability of these anion states.

Low-power control of haze using a liquid-crystal phase-grating device with two-dimensional polymer walls.

We propose a two-dimensional (2D) polymer-walled liquid-crystal (LC) phase-grating device, which can be used to control the haze with a very low power. 2D polymer walls can be formed in an LC cell through ultraviolet light irradiation while applying an in-plane electric field through phase separation induced by the spatial elastic energy difference. The transparent and translucent states can be realized by applying vertical and in-plane electric fields to the 2D polymer-walled LC cell, respectively. The cell can be operated with a very low power as the transparent [translucent] state is maintained even after the applied vertical [in-plane] electric field is removed. It consumes power only during state switching. The fabricated device exhibits outstanding performances, such as a very low operating voltage (< 10 V), low haze (< 2%) in the transparent state, high haze (> 90%) in the translucent state, and short switching time (< 2 ms), compared to those of other bistable LC devices, which can be used to control the haze.

Implementation of analytical gradients and of a mixed real and momentum space DVR method for excess electron systems described by a self-consistent polarization model.

This work presents two extensions of our self-consistent polarization model for treating non-valence excess electron systems. The first extension is the implementation of analytical gradients, and the second extension is the implementation of a mixed real space plus momentum space approach combined with fast Fourier transforms to reduce the computational time compared to a purely real space discrete variable representation approach. The performance of the new algorithms is assessed in calculations of the excess electron states of various size water clusters and of the non-valence correlation-bound anion of the C240 fullerene.

Switching between transparent and translucent states of a two-dimensional liquid crystal phase grating device with crossed interdigitated electrodes.

We report an electrically-switchable two-dimensional liquid crystal (LC) phase grating device for window display applications. The device consists of the top and bottom substrates with crossed interdigitated electrodes and vertically-aligned LCs sandwiched between the two substrates. The device, switchable between the transparent and translucent states by applying an electric field, can provide high haze by the strong diffraction effect thanks to a large spatial phase difference with little dependence on the azimuth angle. We found that the device has outstanding features, such as a low operating voltage, high transparency, and wide viewing angle characteristics in the transparent state and high haze in the translucent state. Moreover, we achieved submillisecond switching between transparent and translucent states by employing the overdrive scheme and a vertical trigger pulse.

A Low Voltage Liquid Crystal Phase Grating with Switchable Diffraction Angles.

We demonstrate a simple yet high performance phase grating with switchable diffraction angles using a fringe field switching (FFS) liquid crystal (LC) cell. The LC rubbing angle is parallel to the FFS electrodes (i.e. α = 0°), leading to symmetric LC director distribution in a voltage-on state. Such a grating exhibits three unique features: 1) Two grating periods can be formed by controlling the applied voltage, resulting in switchable diffraction angles. In our design, the 1st diffraction order occurs at 4.3°, while the 2nd order appears at 8.6°. 2) The required voltage to achieve peak diffraction efficiency (η~32%) for the 1st order is only 4.4 V at λ = 633 nm as compared to 70 V for a conventional FFS-based phase grating in which α ≈ 7°, while the 2nd order (η~27%) is 15 V. 3). The measured rise and decay time for the 1st order is 7.62 ms and 6.75 ms, and for the 2nd order is 0.75 ms and 3.87 ms, respectively. To understand the physical mechanisms, we also perform device simulations. Good agreement between experiment and simulation is obtained.

Interdigitated pixel electrodes with alternating tilts for fast fringe-field switching of liquid crystals.

We propose an interdigitated pixel electrode structure with alternating tilts for fast fringe-field switching of liquid crystals (LCs). In contrast to an LC cell, where the pixel electrodes are parallel to the LC alignment direction, this device does not require a non-zero pretilt angle, owing to an obliquely applied electric field; thus, it can retain a much wider viewing angle by aligning the LCs without a pretilt. In addition to a short response time and wide viewing angle, the proposed device allows a much larger deviation of the LC alignment direction, which is essential for mass production. Moreover, LCs with negative dielectric anisotropy can be used to minimize the transmittance decrease.