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Surface-specific sum frequency generation vibrational spectroscopy is applied to study the molecular configuration of short-chain n-alkanethiol self-assembled monolayers (SAMs with n = 2–6) on the Au surface. For monolayers with n ≥ 3, the alkanethiols are upright-oriented, with the CH3 tilt angle varying between ∼33° and ∼46° in clear even–odd dependency. The ethanethiol monolayer (n = 2) is, however, found to exhibit a distinct lying-down configuration with a larger methyl tilt angle (67°–79°) and a smaller CH2 tilt angle (56°–68°). Such a unique configurational transition from n = 2 to n ≥ 3 discloses the steric effect owing to chain–chain interaction among neighboring molecules. Through density functional theory calculations, the transition is further confirmed to be energetically favorable for thiols on a defective reconstructed Au(111) surface but not on the pristine one. Our study highlights the roles of the chain–chain interaction and the substrate surface atomic structure when organizing SAMs, offering a strategic pathway for exploiting their applications. [ABSTRACT FROM AUTHOR]

This article is a response to criticisms raised by Hirano et al. regarding research on sum frequency vibrational spectroscopy (SFVS) of benzene at interfaces. The authors address five points raised in the comment, including the local field effect, symmetry breaking of benzene, and field variations at interfaces. They argue that Hirano et al. underestimated the interfacial EQ SFVS and did not calculate the absolute amplitude of SFVS, which undermines the credibility of their research. The authors' computational SFVS aligns well with experimental results in terms of vibrational frequencies, amplitude, and line shapes, but there are discrepancies in vibrational frequencies and spectral line shapes between their results and the experimental data. [Extracted from the article]

The solvent effects on the linear and second-order nonlinear optical properties of an aminonaphtylethenylpyridinium (ANEP) dye are investigated by combining experimental and theoretical chemistry methods. On the one hand, deep near infrared (NIR) hyper-Rayleigh scattering (HRS) measurements (1840–1950 nm) are performed on solutions of di-8-ANEPPS in deuterated chloroform, dimethylformamide, and dimethylsulfoxide to determine their first hyperpolarizablity (βHRS). For the first time, these HRS experiments are carried out in the picosecond regime in the deep NIR with very moderate (≤3 mW) average input power, providing a good signal-to-noise ratio and avoiding solvent thermal effects. Moreover, the frequency dispersion of βHRS is investigated for Disperse Red 1 (DR1), a dye commonly used as HRS external reference. On the other hand, these are compared with computational chemistry results obtained by using a sequential molecular dynamics (MD) then quantum mechanics (QM) approach. The MD method allows accounting for the dynamical nature of the molecular structures. Then, the QM part is based on TDDFT/M06-2X/6-311+G* calculations using solvation models ranging from continuum to discrete ones. Measurements report a decrease of the βHRS of di-8-ANEPPS in more polar solvents and these effects are reproduced by the different solvation models. For di-8-ANEPPS and DR1, comparisons show that the use of a hybrid solvation model, combining the description of the solvent molecules around the probe by point charges with a continuum model, already achieves quasi quantitative agreement with experiment. These results are further improved by using a polarizable embedding that includes the atomic polarizabilities in the solvent description. [ABSTRACT FROM AUTHOR]

Second-order nonlinear spectroscopy is becoming an increasingly important technique in the study of interfacial systems owing to its marked ability to study molecular structures and interactions. The properties of such a system under investigation are contained within their intrinsic second-order susceptibilities which are mapped onto the measured nonlinear signals (e.g. sum-frequency generation) through the applied experimental settings. Despite this yielding a plethora of information, many crucial aspects of molecular systems typically remain elusive, for example the depth distributions, molecular orientation and local dielectric properties of its constituent chromophores. Here, it is shown that this information is contained within the phase of the measured signal and, critically, can be extracted through measurement of multiple nonlinear pathways (both the sum-frequency and difference-frequency output signals). Furthermore, it is shown that this novel information can directly be correlated to the characteristic vibrational spectra, enabling a new type of advanced sample characterization and a profound analysis of interfacial molecular structures. The theory underlying the different contributions to the measured phase of distinct nonlinear pathways is derived, after which the presented phase disentanglement methodology is experimentally demonstrated for model systems of self-assembled monolayers on several metallic substrates. The obtained phases of the local fields are compared to the corresponding phases of the nonlinear Fresnel factors calculated through the commonly used theoretical model, the three-layer model. It is found that, despite its rather crude assumptions, the model yields remarkable similarity to the experimentally obtained values, thus providing validation of the model for many sample classes. [ABSTRACT FROM AUTHOR]

Using Bayesian spectroscopy, we performed spectral decomposition of gate modulation (GM) spectra measured in a pentacene organic field-effect transistor to understand comprehensively the optical nonlinear response due to GM and hole injection. Although GM spectra contain a variety of spectral components, by Bayesian spectroscopy, we can specify the role of each component in the nonlinear response by performing model selection that chooses the spectral components needed to explain the data without preconceptions. For a GM spectrum under positive GM, Bayesian spectroscopy shows that nonlinear responses by the change in polarizability dominate the GM spectrum among several types of Stark signals induced by the GM electric field, which is a physically valid conclusion. For GM spectra under negative GM where gate-induced carriers are injected, Bayesian spectroscopy succeeds in completely elucidating the spectral structure, which is composed of the two types of Stark signals due to changes in the polarizability and the dipole moment, bleaching, and gate-induced absorption signals. A pentacene film is known to have solid and isolated molecular phases, which may give different spectral responses. Therefore, we compared a model that treats these responses equally and a model that distinguishes them. Bayesian spectroscopy selects the latter models for all GM spectra, revealing statistically that nonlinear optical effects and hole injection effects are different in these phases. [ABSTRACT FROM AUTHOR]

Nonlinear spectroscopy with quantum entangled photons is an emerging field of research that holds the promise to achieve superior signal-to-noise ratio and effectively isolate many-body interactions. Photon sources used for this purpose, however, lack the frequency tunability and spectral bandwidth demanded by contemporary molecular materials. Here, we present design strategies for efficient spontaneous parametric downconversion to generate biphoton states with adequate spectral bandwidth and at visible wavelengths. Importantly, we demonstrate, by suitable design of the nonlinear optical interaction, the scope to engineer the degree of spectral correlations between the photons of the pair. We also present an experimental methodology to effectively characterize such spectral correlations. Importantly, we believe that such a characterization tool can be effectively adapted as a spectroscopy platform to optically probe system–bath interactions in materials. [ABSTRACT FROM AUTHOR]

This study presents a focused investigation and comprehensive analysis of the synthesis of hybrid Polyaniline/Cobalt ferrite (PANI/CoFe 2 O 4) nanocomposites using an optimized electrochemical polymerization method. CoFe 2 O 4 nanoparticles (NPs) were incorporated into the PANI matrix at varying concentrations (3, 6, and 12 wt%). The research examined the newly synthesized hybrid nanocomposites in terms of their structure, dielectric properties, and both linear and nonlinear optical properties. As a result of the Williamson-Hall method, the average crystallite size varied between 45 and 99 nm. Initially, adding a small quantity of NPs decreased the nanocomposite size, but further additions increased it due to aggregation. The Tauc plot showed a gradual increase in the energy band gap of the films as the concentration of CoFe 2 O 4 NPs increased up to 12 wt%. This trend showed stronger absorption bands and higher coefficients, indicating improved light absorption compared to pure PANI films. Dielectric properties, including dielectric constants (ɛr, ɛi) and dielectric loss (tan δ), were examined as a function of frequency. The experimental results indicated that PANI/CoFe2O4 exhibited lower dielectric constants than bare PANI. Concentration-dependent optical properties, such as electronic transition excitation energies, dispersion energies, and optical conductivity, were also investigated. These properties were modeled using a single oscillator based on the Wemple-DiDomenico (WDD) approach. The study revealed a reduction in key optical parameters—linear susceptibility, nonlinear third-order susceptibility, and nonlinear refractive index—as nanoparticle content increased. Conversely, increasing concentrations of CoFe 2 O 4 NPs led to a significant increase in the ratio of free carriers to effective mass (N/m٭), from 3.89 × 10³⁶ to 4.04 × 10³⁶ m⁻³ kg⁻1. Additionally, the electrical conductivity of both PANI and PANI/CoFe2O4 nanocomposites exhibited temperature-dependent improvement, reaching maximum values. The observed findings indicate that hybrid PANI-CoFe2O4 nanocomposites possess enhanced properties, highlighting their promising potential as active materials for a broad range of optoelectronic applications. [ABSTRACT FROM AUTHOR]

This study pioneers a novel strategy for synthesizing solar‐blind ultraviolet (UV) nonlinear optical (NLO) crystals through functional groups sequential construction, effectively addressing the inherent trade‐offs among broad transmittance, enhanced second‐harmonic generation (SHG), and optimal birefringence. We have developed two innovative van der Waals layered germanous phosphites: GeHPO3, the first Ge(II)‐based oxide NLO crystal which exhibits a black phosphorus‐like structure, and K(GeHPO3)2Br, distinguished by its exceptional birefringence and graphene‐like structure. Significantly, GeHPO3 exhibits a remarkable array of NLO properties, including the highest SHG coefficient recorded among all NLO crystals for phase‐matching and generating 266 nm coherent light via quadruple frequency conversion. It delivers a potent SHG intensity, surpassing KH2PO4 (KDP) by 10.3 times at 1064 nm and β‐BaB2O4 by 1.3 times at 532 nm, complemented by a distinct UV absorption edge at 211 nm and moderate birefringence of 0.062 at 546 nm. Comprehensive theoretical analysis links these exceptional characteristics to the unique NLO‐active GeO34− units and the distinctive, highly ordered layered structures. Our findings deliver essential experimental insights into the development of Ge(II)‐based optoelectronic materials and present a strategic blueprint for engineering structure‐driven functional materials with customized properties. [ABSTRACT FROM AUTHOR]

This work focuses on the electronic, optoelectronic, and nonlinear optical properties of the cyclo[2N]carbon series (C10, C12, C14, C16, C18, C20, C22, and C24), and their derivative systems (C8BN, C10BN, C12BN, C14BN, C16BN, C18BN, C20BN, and C22BN) obtained by functionalizing each molecule of the series with the boron–nitrogen (B–N) binomial. The results were obtained from density functional theory and time-dependent density functional theory at the B3LYP-D3, CAM-B3LYP-D3, and ωB97XD/6–31 + G(d) levels of theory. The study found that the cumulative B–N effects on the molecules studied break the centrosymmetry of these molecules while, lowering the energy gap (from 3.11 eV for C18 to 2.80 eV for its derivative C16BN) making these molecules good materials for electronics. The C2N molecules (2N = 4n), namely C12, C16, C20, and C24, and their derivatives C10BN, C14BN, C18BN, and C22BN, are found to have high chemical softness (s), electronegativity (η), and electrophilic index (ω), making them useful materials in optoelectronics. An impressive impact of the B–N cumulative effect on the cyclo[2N]carbon's series is that it significantly generates the first-order hyperpolarizability values. Like C24 of which β = 0.00 a.u. and its derivative C22BN of which β = 8812.77 a.u., value 8 times higher than that of paranitroaniline (β = 1072.44 a.u.), which is the reference compound in nonlinear optics, rendering these molecules interesting for linear and non-linear optical applications. [ABSTRACT FROM AUTHOR]

The linear and nonlinear optical properties of metallic nanoparticles have attracted considerable experimental and theoretical research interest. To date, most researchers have focused primarily on exploiting their plasmon excitation enhanced near-field and far-field responses and related applications in sensing, imaging, energy harvesting, conversion, and storage. Among numerous plasmonic structures, nanoparticle dimers, being a structurally simple and easy-to-prepare system, hold significant importance in the field of nanoplasmonics. In highly symmetric plasmonic nanostructures, although the odd-order optical nonlinearity of the near-surface region will be improved because of the enhanced near-fields, even-order nonlinear processes such as second-harmonic generation (SHG) will still be quenched and thus optically forbidden. Under this premise, it is imperative to introduce structural symmetry breaking to realize plasmon-enhanced even-order optical nonlinearity. Here, we fabricate a series of nanoparticle dimers each composed of two gold nanospheres with different diameters and subsequently investigate their structural asymmetry dependent linear and nonlinear optical properties. We find that the SHG intensities of gold nanosphere dimers are significantly enhanced by structural asymmetry under off-resonance excitation while the plasmonic near-field enhancement mainly affects SHG under on-resonance excitation. Our results reveal that symmetry breaking will play an indispensable role when designing novel coupled plasmonic nanostructures with enhanced nonlinear optical properties. [ABSTRACT FROM AUTHOR]

Coherent anti-Stokes Raman Scattering (CARS) spectroscopy is a nonlinear optical technique that is used to investigate many different chemical and biological systems. This tool is very efficient and essentially completely rejects fluorescence. As is well known, the excitation profiles of resonance CARS are mostly used to estimate the origin shift parameters with electronic excitation for vibrations with resonantly enhanced Raman components that give information about the molecular structure and its changes in an excited electronic state. Certainly, it is necessary to have an appropriate theoretical model for pragmatically representing these processes and considering the joint (simultaneous) impact of different broadening mechanisms. The theoretical model presented in the paper is the most general and is free from a priori assumptions. Also, the mathematical algorithm created on its basis is flexible and fast for quantitative calculations. [ABSTRACT FROM AUTHOR]

Although interfacial solvation plays an important role in determining carbon dioxide reduction (CO2R) kinetics, present understanding of the potential dependent properties of the electrochemical double layer under conditions relevant for CO2R remains limited. This article summarizes the development and recent applications of plasmon‐enhanced vibrational sum frequency generation (VSFG) spectroscopy to study the effects of cation hydration and interfacial solvation on CO2R using CO as a vibrational Stark reporter. Results show that electrolyte cations retain their entire solvation shell upon adsorption to inactive sites, while active sites retain only a single water layer between the gold surface and the cation. Measurements also show that the total interfacial electric field can be separated into two contributions: one from the electrochemical double layer (Stern field) and another from the polar solvation environment (Onsager field). Surprisingly, correlating VSFG spectra with reaction kinetics reveals that it is the solvation‐mediated Onsager field that governs the chemical reactivity at the electrode/electrolyte interface. Measuring the interfacial water spectra during electrocatalysis also provides evidence for the proton source during H2 evolution, which competes with CO2R in aqueous electrolyte. These findings highlight the importance of directly probing cation hydration and interfacial solvation, which mediates reaction kinetics at electrochemical interfaces. [ABSTRACT FROM AUTHOR]

Organic–inorganic 2D heterostructures combine the high optical absorption of organic molecules with exciton‐dominated optical properties in layered transition metal dichalcogenides (TMDs) such as MoS2. Critical to the interaction and the optical response in such hybrid systems is the electronic band alignment at the interface between the two species. Here, the coupling of monolayers of perylene derivatives is investigated with bilayer MoS2. In particular, variation in the perylene orientation on the MoS2 surface is identified using Raman spectroscopy and scanning probe microscopy. Low‐temperature optical spectroscopy reveals orientation‐dependent interlayer exciton formation. Furthermore, power‐dependent photoluminescence measurements provide insight into the modified interlayer charge transfer in these heterostructures. A saturation of interlayer states is found under high excitation power when the perylene molecules are in a perpendicular orientation to the surface that leads to electron accumulation in the MoS2, whereas parallel alignment of the perylene molecules leads to enhanced populations of organic–inorganic interlayer excitons. This work provides insights into the optimization of organic–inorganic heterostructures, with particular relevance to applications for optoelectronic and excitonic devices. [ABSTRACT FROM AUTHOR]

The vibrational dynamics of the NO stretching mode of [RuCl5(NO)]2− in D2O were investigated by nonlinear infrared (IR) spectroscopy. We performed IR pump–probe measurements to obtain the vibrational lifetime of this molecule. The lifetime is 31 ps, which is sufficiently long enough to study the vibrational frequency fluctuation on a slower time scale with high precision. By two-dimensional IR spectroscopy, the frequency–frequency time correlation function (FFTCF) of the NO stretching mode was characterized with a delta function plus a double-exponential function. The time constant of the slower component was ∼10 ps. We also found that the time constant does not strongly depend on temperature. In order to investigate the microscopic origin of this component, we performed classical molecular dynamics simulations. It was found that the hydration structure around the NO group was influenced by the negatively charged Cl ligands. To calculate the FFTCF decay, we employed an approximate theoretical model based on the vibrational solvatochromism theory. It was demonstrated that water fluctuations around the Cl ligands projected on the NO group correspond to the 10 ps decay component in the FFTCF. The fluctuation is related to the orientational dynamics of the water molecules attracted by the Cl ligands. By comparing the FFTCF parameters of the present solute with those of previously reported metal complexes and SCN− in D2O, we conclude that the presence of different electrostatic environments around the vibrational probe and the other interaction sites of the solute is important for understanding the slow decay component in the FFTCFs. [ABSTRACT FROM AUTHOR]

FTIR, FT-Raman and NMR are studied to explore the functional groups, the vibration modes and its coupling interactions for the grown single crystal piperazine-1,4-diium bis (4-aminobenzenesulfonate) (PABS). The cut-off wavelength at 303 nm of UV–Visible spectrum exhibits great transmittance over the entire visible spectrum. Photoluminescence spectral study revealed the electron excitation notably in blue emission range. The range of susceptibility and nonlinear refractive index was obtained from second and third harmonic generations of PABS crystals. At various temperatures, the thermal stability of the crystal and the crystal dielectric characteristics had been studied in relation to frequency. The hardness of the crystal was obtained by microhardness measurements. [ABSTRACT FROM AUTHOR]

Due to their strong molecular hyperpolarizability, organic push–pull materials are gaining interest for nonlinear optical applications. We were able to characterize the intramolecular charge transfer and the distribution of the electron cloud within the molecular unit by exciting these materials under the influence of an electric field. The series products of conjugated monomers derived from acrylo–azobenzene containing in the para position the attracting groups (–H, –NO2, –COOC2H5, –SO3H and –COOH) exhibit good nonlinear optical activity. We computed the nonlinear optical characteristics of these compounds as well as exploiting the theoretical calculations of DFT and AM1 to determine their hyperpolarizabilities. Besides, we investigated the increase in hyperpolarizability in the push–pull model of organic compounds under the effect of the strength of attracting groups, the existence of the conjugated π -electron and the azo bridge. [ABSTRACT FROM AUTHOR]

Coherent nonlinear optical μ -spectroscopy is a frequently used tool in modern material science as it is sensitive to many different local observables, which comprise, among others, crystal symmetry and vibrational properties. The richness in information, however, may come with challenges in data interpretation, as one has to disentangle the many different effects like multiple reflections, phase jumps at interfaces, or the influence of the Guoy-phase. In order to facilitate interpretation, the work presented here proposes an easy-to-use semi-analytical modeling Ansatz, which bases upon known analytical solutions using Gaussian beams. Specifically, we apply this Ansatz to compute nonlinear optical responses of (thin film) optical materials. We try to conserve the meaning of intuitive parameters like the Gouy-phase and the nonlinear coherent interaction length. In particular, the concept of coherence length is extended, which is a must when using focal beams. The model is subsequently applied to exemplary cases of second- and third-harmonic generation. We observe a very good agreement with experimental data, and furthermore, despite the constraints and limits of the analytical Ansatz, our model performs similarly well as when using more rigorous simulations. However, it outperforms the latter in terms of computational power, requiring more than three orders less computational time and less performant computer systems. [ABSTRACT FROM AUTHOR]

Established on the appealing properties of borate glass, a new magnesium borate glass of definite composition (56 − x)B2O3–40Na2O–4MoO3–xMgO (x = 0, 2, 4, 8 mol. %) is prepared via the melt quenching technique. The present study clarified the consequence of dopant and co-dopant on the borate glass. Different physical properties are sustained to investigate and explain the optical and electrical properties of the obtained glass as a result of the replacement of B2O3 by MgO. FTIR confirmed the conversion of MgO6 into MgO4. The index of refraction increased is accompanied by a decrease in bandgap energy. At a frequency of 0.1 Hz, the ac-conductivity varies between 4 and 20 pS/cm at 25 °C and between 10 and 30 nS/cm at 150 °C without the systematic effect of MgO concentration, which indicates that heating plays the main role in improving conductivity. The metallization criterion is between 0.41 and 0.425. The computed two-photon absorption values ranged from 5.313 to 8.391 cm/GW; therefore, it is recommended that the prepared glasses are ideal for optical signal-processing equipment and are considered promising as a new member of the nonlinear optical glass. [ABSTRACT FROM AUTHOR]

Tuning of intramolecular charge transfer (ICT) in a molecule could be used to modulate its linear and nonlinear optical (NLO) response properties. Over the years, the ICT process in the so-called "push–pull" molecules in which electron donor (D) and acceptor (A) groups are connected either directly or through a π-electron bridge has been used for emission color tuning, modulating absorption maxima, optimizing first or higher order hyperpolarizabilities, and two-photon absorption (TPA), among others. As ICT is the functional basis of many optoelectronic and semiconductor devices, optimizing the parameters involved in this process as well as modeling the effect of the environment and intermolecular interaction are crucial for these applications. NLO processes such as second harmonic generation, sum-frequency generation, and TPA have been used extensively for numerous technological applications, such as optical switching, optical limiting, bioimaging, and biophotonics. Recently, through-bond and through-space ICT have been employed to tune the reverse intersystem crossing that facilitates thermally activated delayed fluorescence for fabricating next-generation organic light-emitting diodes. Aggregation-induced emission of ICT molecules either alone or in combination with the other phenomenon, such as TPA, could be useful in many optical applications. In this perspective, the state-of-the-art and challenges in designing ICT-based molecules and materials for optical applications will be discussed. The underlying theories used to quantify the magnitude of ICT and NLO response are mentioned, followed by a discussion on the latest development and scope of using these molecules and materials for optical applications. [ABSTRACT FROM AUTHOR]

We evidence the ferroelectricity of two isostructural magnetic coordination networks obtained from a chiral imidazolium dicarboxylate salt ((S, S)‐1,3‐bis(1‐carboxylethyl)imidazolium or [HL*]) and Gd3+ or Dy3+ ions in presence of oxalic acid (H2ox). The two compounds exhibit a chiral structure P1 and ferroelectric properties. The crystallographic study shows that the Dy based‐compound is isostructural to the Gd analog. The non‐centrosymmetry of the two samples was further checked by means of nonlinear optical spectroscopy. The room temperature ferroelectric character of the compounds has been investigated through by an original method, derived from that used for thin films, made possible by preparing the sample as thin slices of resin containing inclusions of the coordination compounds. [ABSTRACT FROM AUTHOR]

Experimental insight into the elementary processes underlying charge transfer across interfaces has blossomed with the wide-spread availability of ultra-high vacuum (UHV) setups that allow the preparation and characterization of solid surfaces with well-defined molecular adsorbates over a wide range of temperatures. Within the last 15 years, such insights have extended to charge transfer heterostructures containing solids overlain by one or more atomically thin two dimensional materials. Such systems are of wide potential interest both because they appear to offer a path to separate surface reactivity from bulk chemical properties and because some offer completely novel physics, unrealizable in bulk three dimensional solids. Thick layers of molecular adsorbates or heterostructures of 2D materials generally preclude the use of electrons or atoms as probes. However, with linear photon-in/photon-out techniques, it is often challenging to assign the observed optical response to a particular portion of the interface. We and prior workers have demonstrated that by full characterization of the symmetry of the second order nonlinear optical susceptibility, i.e., the χ(2), in sum frequency generation (SFG) spectroscopy, this problem can be overcome. Here, we describe an UHV system built to allow conventional UHV sample preparation and characterization, femtosecond and polarization resolved SFG spectroscopy, the azimuthal sample rotation necessary to fully describe χ(2) symmetry, and sufficient stability to allow scanning SFG microscopy. We demonstrate these capabilities in proof-of-principle measurements on CO adsorbed on Pt(111) and on the clean Ag(111) surface. Because this setup allows both full characterization of the nonlinear susceptibility and the temperature control and sample preparation/characterization of conventional UHV setups, we expect it to be of great utility in the investigation of both the basic physics and applications of solid, 2D material heterostructures. [ABSTRACT FROM AUTHOR]

Multipartite quantum entanglement plays a vital role in both fundamental science and quantum applications. The cascaded four‐wave mixing (FWM) process is an effective method to prepare multipartite entanglement, however, the physical nature of entanglement based on different cascading paths, i.e., simultaneous cascaded FWM (SC‐FWM) and ordinal cascaded FWM (OC‐FWM), has not yet been conclusively determined. In this article, tunable continuous‐variable (CV) triple‐mode entanglement is proposed to be generated by using both the SC‐FWM and OC‐FWM schemes. The simulation results reveal that the absorption/dispersion properties of the two nonlinear processes can be efficiently tuned by varying the optical parameters (i.e., the photon detuning and the nonlinear susceptibility), resulting in triple‐mode CV entanglement with tunable properties. Compared with the OC‐FWM scheme, the SC‐FWM scheme has a broader entanglement bandwidth and a higher degree of entanglement, where the tripartite entanglement region is 4.38% larger than that of the OC‐FWM scheme. Furthermore, these results indicate that the SC‐FWM scheme has a more compact and stable mode structure with better entanglement performance. Such tunable optical triple‐mode entanglement may find applications in specific quantum communication protocols and pave the way for implementing and manipulating multichannel quantum networks. [ABSTRACT FROM AUTHOR]

Noise manifests ubiquitously in nonlinear spectroscopy, where multiple sources contribute to experimental signals generating interrelated unwanted components, from random point-wise fluctuations to structured baseline signals. Mitigating strategies are usually heuristic, depending on subjective biases such as the setting of parameters in data analysis algorithms and the removal order of the unwanted components. We propose a data-driven frequency-domain denoiser based on a convolutional neural network to extract authentic vibrational features from a nonlinear background in noisy spectroscopic raw data. The different spectral scales in the problem are treated in parallel by means of filters with multiple kernel sizes, which allow the receptive field of the network to adapt to the informative features in the spectra. We test our approach by retrieving asymmetric peaks in stimulated Raman spectroscopy, an ideal test-bed due to its intrinsic complex spectral features combined with a strong background signal. By using a theoretical perturbative toolbox, we efficiently train the network with simulated datasets resembling the statistical properties and lineshapes of the experimental spectra. The developed algorithm is successfully applied to experimental data to obtain noise- and background-free stimulated Raman spectra of organic molecules and prototypical heme proteins. [ABSTRACT FROM AUTHOR]

The utilization of ionic liquids as versatile reaction media and catalysts has garnered significant attention in the field of green and sustainable chemistry. In this study, sum frequency generation vibrational spectroscopy (SFG-VS) is employed to investigate the interactions between l-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) and styrene oxide (SO) at the air/liquid interface. Spectral analysis in the range of 1000 cm−1 to 3700 cm−1 reveals that only vibrational modes of C–H bonds are observed. Notably, the orientation of the epoxy ring of SO is found to be towards the bulk phase, while the three C–H groups on the imidazolium ring of the cation are parallel to the surface. Consequently, there are no observed interactions between the cation and SO. However, in the vibrational spectra of C–H bonds, interactions between the anion BF4- and the CH2 group of the epoxy ring result in blue shifts in the vibrations of CH (SO) and CH3 (cation). These findings support a proposed reaction mechanism where the ionic liquid catalyzes SO first and subsequently reacts with CO2 providing valuable insights into intermolecular interactions and molecular orientations at reaction interfaces. [ABSTRACT FROM AUTHOR]

The surface states of photoelectrodes as catalysts heavily influence their performance in photocatalysis and photoelectrocatalysis applications. These catalysts are necessary for developing robust solutions to the climate and global energy crises by promoting CO2 reduction, N2 reduction, contaminant degradation, and water splitting. The semiconductors that can fill this role are beholden as photoelectrodes to the processes of charge generation, separation, and utilization, which are in turn products of surface states, surface electric fields, and surface carrier dynamics. Methods which are typically used for studying these processes to improve semiconductors are indirect, invasive, not surface specific, not practical under ambient conditions, or a combination thereof. Recently, nonlinear optical processes such as electronic sum-frequency generation (ESFG) and second-harmonic generation (ESHG) have gained popularity in investigations of semiconductor catalysts systems. Such techniques possess many advantages of in-situ analysis, interfacial specificity, non-invasiveness, as well as the ability to be used under any conditions. In this review, we detail the importance of surface states and their intimate relationship with catalytic performance, outline methods to investigate semiconductor surface states, electric fields, and carrier dynamics and highlight recent contributions to the field through interface-specific spectroscopy. We will also discuss how the recent development of heterodyne-detected ESHG (HD-ESHG) was used to extract charged surface states through phase information, time-resolved ESFG (TR-ESFG) to obtain in-situ dynamic process monitoring, and two-dimensional ESFG (2D-ESFG) to explore surface state couplings, and how further advancements in spectroscopic technology can fill in knowledge gaps to accelerate photoelectrocatalyst utilization. We believe that this work will provide a valuable summary of the importance of semiconductor surface states and interfacial electronic properties, inform a broad audience of the capabilities of nonlinear optical techniques, and inspire future original approaches to improving photocatalytic and photoelectrocatalytic devices. [ABSTRACT FROM AUTHOR]

A new noncentrosymmetric strontium borate, P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O (1), has been synthesized under the hydrothermal condition. The P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O shows a layered B−O network with 9‐ring windows in the ab plane. Sr2+ cations, H3BO3, and H2O molecules are located in the voids of layers and interlayers, respectively. The P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O is the first synthetic phase of veatchite, while the other three polymorphs are found in different natural minerals. This strontium borate is a potential deep‐ultraviolet‐transparent nonlinear‐optical (NLO) crystal whose second‐harmonic‐generation (SHG) intensity is 1.7 times that of KH2PO4 (KDP) and is phase‐matchable. The short wavelength cutoff edge of compound 1 is below 190 nm. Density functional theory (DFT) calculations show that the B−O units are responsible for the nonlinear optical property. [ABSTRACT FROM AUTHOR]

An original series of bipyrimidine‐based chromophores featuring alkoxystyryl donor groups bearing short chiral (S)‐2‐methylbutyl chains in positions 4, 3,4 and 3,5, connected to electron‐accepting 2,2‐bipyrimidine rings, has been developed. Their linear and non‐linear optical properties were studied using a variety of techniques, including one‐ and two‐photon absorption spectroscopy, fluorescence measurements, as well as Hyper‐Rayleigh scattering to determine the first hyperpolarizabilities. Their electronic and geometrical properties were rationalized by TD‐DFT calculations. The thermal properties of the compounds were also investigated by a combination of polarized light optical microscopy, differential scanning calorimetry measurements and small‐angle X‐ray scattering experiments. The derivatives were found not to have mesomorphic properties, but to exhibit melting temperatures or cold crystallization behavior that enabled the isolation of well‐organized thin films. The nonlinear optical properties of amorphous or crystalline thin films were studied by wide‐field second harmonic generation and multiphoton fluorescence imaging, confirming that non‐centrosymmetric crystal organization enables strong second and third harmonic generation. This new series confirms that our strategy of functionalizing 3D organic octupoles with short chiral chains to generate non‐centrosymmetric organized thin films enables the development of highly second order nonlinear optical active materials without the use of corona‐poling or tedious deposition techniques. [ABSTRACT FROM AUTHOR]

The work aims to investigate the nonlinear optical (NLO) activity of piperazine‐1,4‐diium acetate (PAA) molecule utilizing computational techniques. The computational calculations are performed using density functional theory (DFT) to explore the vibrational modes, electronic and NLO properties of PAA by comparing them with piperazine and acetic acid molecules. The natural bond orbital analysis is performed to identify hydrogen bonding and charge transfer interaction. A vibrational analysis is carried out and the assignment of fundamental modes is done using the vibrational energy distribution analysis (VEDA) program. Molecular electrostatic potential, frontier molecular orbital, electron localization function, localized orbital locator and Fukui analysis are carried out to identify chemical reactivity and charge transfer interaction. The UV–visible analysis is performed to obtain the electronic absorption spectrum. The hole–electron analysis is performed for the first five excitations to identify the type of excitation. The atoms in molecules, reduced density gradient and independent gradient model are performed to identify the hydrogen bonding, steric and van der Waals interactions. Hirshfeld analysis is performed to explore the intermolecular interactions within the PAA molecule. The NLO calculation is performed to evaluate the NLO parameters. The obtained results show that the PAA molecule is suitable for NLO applications. [ABSTRACT FROM AUTHOR]

The helical structure is a classical framework to design high-performance organic electro-optical materials. In this work, the structure-property's relationships of helical tetraspirobenzene (1) and its oxidation (12+) and reduction (12–) products are explored. The results show that the redox brings some distinctive changes in their geometric structure and electronic property, which regulate the first hyperpolarisability (βtot). Among these structures, the 12– has the largest βtot value of 4.2 × 104, which is greatly larger than 2.0 × 102 a.u. of. 12+. Therefore, the reduction effect is more obvious than the oxidation effect. Furthermore, the UV-Vis absorption spectrum also proves this phenomenon: the oxidation product has a new red-shifted absorption peak (571 nm) and the reduction product has two new red-shifted absorption peaks (577 and 797 nm). We hope the present work can provide theoretical guidance for the search for high-performance nonlinear optical materials by using the redox effect. [ABSTRACT FROM AUTHOR]

Chirped pulse amplification (CPA) has been a commonly used methodology to obtain powerful ultrashort laser pulses ever since its first demonstration. However, wavelength-tunable CPA systems are much less common. Wavelength-tunable ultrashort and intense laser pulses are desirable in various fields such as nonlinear spectroscopy and optical parametric amplification. In this work, we report a 1720 nm–1800 nm tunable CPA system based on Tm-doped fiber. The tunable CPA system contains a seed laser, a pulse stretcher, two cascaded amplifiers and a pulse compressor. The dispersion-managed seed laser cavity emits wavelength-tunable laser pulses with pulse durations of several ps and spectral widths from 25 nm to 34 nm. After being stretched temporally to tens of ps, the laser pulses are then amplified in two-stage amplifiers and compressed in a Treacy-type compressor. At 1720 nm, the maximum average power of 126 mW is obtained with a pulse duration of 507 fs; at 1800 nm, the maximum average power of 264 mW is obtained with a pulse duration of 294 fs. The pulse repetition rates are around 22.7 MHz. We perform an analysis of the system design based on numerical simulations and go on to suggest further steps for improvement. To the best of our knowledge, this is the first demonstration of a tunable CPA system beyond 1.1 μm. Considering the specific wavelength range, this wavelength-tunable CPA system is highly desirable for biomedical imaging, sensing, and parametric amplifiers. [ABSTRACT FROM AUTHOR]

Nonlinear optics has generated a wide range of applications in the fields of optical communications, biomedicine, and materials science, with nonlinear conversion efficiency serving as a vital metric for its progress. However, the weak nonlinear response of materials, high optical loss, and inhomogeneous distribution of the light field hamper the improvement of the conversion efficiency. We present a composite grating waveguide structure integrated into a Bragg reflector platform. This design achieves high Q in the spectral range by exploiting the unique properties exhibited by the bound states in the Bloch surface wave-enhanced continuum, and efficient second-harmonic generation by close-field amplification with the optical field tightly localized in a nonlinear material. By manipulating the symmetry of the grating, a precise tune over the near field within a designated wavelength range can be achieved. Specifically, we select a photonic crystal configuration supporting surface waves, employing TE polarization conditions and an asymmetry factor of −0.1 between the composite gratings. This configuration resonates at a fundamental wavelength of 783.5 nm, exhibiting an impressive Q-factor of 106. Notably, at an incident light intensity of 1.33 GW/cm2, we achieve a normalized electric field strength of up to 940 at the fundamental frequency and a second-harmonic conversion efficiency of up to 6 × 10−3, significantly amplifying the second-harmonic response. The proposed configuration in this investigation has the potential to be integrated into the field of nonlinear optics for sensing frequency conversion applications. [ABSTRACT FROM AUTHOR]

This study revisits a (001)-oriented layered lead chloride templated by 1,2,4-triazolium, Tz2PbCl4, which recently has been an object of intense research but still suffers from gaps in characterization. Indeed, the divergent reports on the crystal structures of Tz2PbCl4 at various temperatures, devoid of independent verification of chiral phases through second harmonic generation (SHG), have led to an unresolved debate regarding the existence of a low-temperature phase transition (PT) and the noncentrosymmetric nature of the low-temperature phase. Now, by combining differential scanning calorimetry, single-crystal X-ray diffraction, dielectric, as well as linear and nonlinear optical spectroscopies on Tz2PbCl4, we reveal a sequence of reversible PTs at T1 = 361 K (phase I–II), T2 = 339 K (phase II–III), and T3 = 280 K (phase III–IV). No SHG activity could be registered for any of the four crystal phases, as checked by wide-temperature range SHG screening, supporting their centrosymmetry. The dipole relaxation processes indicate a decrease in activation energy with increasing temperature, from 0.60, 0.38, to 0.24 eV observed for phase IV (space group P21/c), phase III (Pnma), and phase II (Cmcm), respectively. This change is interpreted as a result of the diminishing strength of H-bonds as the system transforms from phase IV to III and subsequently to II. The weaker H-bonds facilitate the reorientation of Tz+ cations in the presence of an external electric field. The photoluminescence spectra of Tz2PbCl4 reveal an intriguing interplay of narrow and broadband emission, linked respectively to free excitons and excitons trapped on defects. Notably, as the temperature decreases from 300 K to 16 K, both the emission bands exhibit distinctive blue and red shifts, indicative of increased in-plane octahedral distortion. This dynamic behaviour transforms the photoluminescence of Tz2PbCl4 from greenish-blue at 300 K to yellowish-green at 13 K, enriching our understanding of 2D lead halide perovskites and highlighting the optoelectronic potential of Tz2PbCl4. [ABSTRACT FROM AUTHOR]

The construction of multifunctional metal-organic frameworks (MOFs) has attracted considerable attention. Two novel Dy-MOFs namely [Dy2(TPTC-2OMe)1.5(H2O)4·H2O]n (1) and {[Dy2(TPTC-2OMe)(H2TPTC-2OMe) (H2O)2]·2H2O}n (2) were obtained by a solvothermal method using 2′,5′-dimethoxy-[1,1′:4′,1″-terphenyl]- 4,4″-dicarboxylic acid (H4TPTC-2OMe) as the ligand. Structure analysis demonstrates that both MOFs 1 and 2 displayed three-dimensional framework structures, in which MOF 1 was with Dy(III) metal chains as nodes, while MOF 2 was with Dy2 binuclear metal clusters as nodes. Interestingly, MOFs 1 and 2 exhibited high thermal and chemistry stabilities and presented relatively high proton conductivity (σ) values of 1.69 × 10-4 S cm-1 and 3.52 × 10-6 S cm-1 at 50 °C and 98% RH. Although there exist a large number of coordinated or free H2O molecules in both structures, it is easier to form an ordered hydrogen-bonding network between the coordinated H2O molecules in the structure of MOFs, resulting in a more excellent proton conductivity of MOF 1. Moreover, MOF 1 exhibited field-induced single-molecule magnet (SMM) behavior with energy barriers (Ueff) of 37.22 K (τ0 = 9.27 × 10-8 s). Furthermore, MOF 1 exhibits obvious second-order nonlinear optical properties. This research provides guidance for the design of novelty multifunctional MOF materials. [ABSTRACT FROM AUTHOR]

Sixty years ago, Reddy, Devanatan, and Bockris performed the first in situ electrochemical ellipsometry experiment, which ushered in a new era in the study of electrochemistry, using optical spectroscopy. After six decades of development, electrochemical optical spectroscopy, particularly electrochemical vibrational spectroscopy, has advanced from a phase of immaturity with few methods and limited applications to a phase of maturity with excellent substrate generality and significantly improved resolutions. Here, we divide the development of electrochemical optical spectroscopy into four phases, focusing on the proof-of-concept of different electrochemical optical spectroscopy studies, the emergence of plasmonic enhancement-based electrochemical optical spectroscopic (in particular vibrational spectroscopic) methods, the realization of electrochemical vibrational spectroscopy on welldefined surfaces, and the efforts to achieve operando spectroelectrochemical applications. Finally, we discuss the future development trend of electrochemical optical spectroscopy, as well as examples of new methodology and research paradigms for operando spectroelectrochemistry. [ABSTRACT FROM AUTHOR]

The present work is aimed at studying how spatially periodic modulations of the refractive index of the medium, i.e., laser-induced gratings (LIGs), generated in a gas mixture containing methane (CH4) by nanosecond pulses of resonant mid-infrared laser radiation, can be used to measure various gas parameters. It is investigated to what extent the temporal profiles of the LIG signals, recorded as the power of the diffracted by LIGs continuous wave probe radiation, are specific to the composition, pressure, and temperature of a selected buffer gas. This specificity is illustrated by the LIG signal profiles recorded in the experiments in different gas mixtures under various conditions. Experimental data show that large LIG signals can be obtained even in mixtures with CH4 concentrations as low as ∼100 parts per million due to the strong absorption of the excitation light and subsequent rapid, highly exothermic, and partner-dependent collisional energy exchange of the laser-excited molecules with the environment. These two factors ensure high LIG generation efficiency by a small number of CH4 molecules and high sensitivity of signal strength and profile to variations of gas parameters. [ABSTRACT FROM AUTHOR]

Developing highly effective nonlinear optical (NLO) materials is a cutting-edge field of study. The desirability of promising NLO materials for optoelectronic and electronic applications drove us to investigate the sulflower (C18S9) doped complexes for developing highly efficient NLO materials. A successful computational design technique for superhalogens (BeF3, MgF3, CaF3, CaCl3) doping is employed on sulflower, and eight stable isomers (BeF3@SF-5M, BeF3@SF-9M, MgF3@SF-5M, MgF3@SF-9M, CaF3@SF-5M, CaF3@SF-9M, CaCl3@ SF-5M, CaCl3@SF-9M) are proposed for NLO properties. DFT and TD-DFT simulations confirm the potential use of superhalogen-doped sulflower complexes for NLO response applications by evaluating NLO response properties, photophysical aspects, frontier molecular orbital (FMO), natural bond orbitals (NBO), non-covalent interaction (NCI), vertical ionization energies (VIE), interaction energies (Eint), molecular electrostatic potential (MEP) and density of state (DOS) analysis. The Eint (−28.37 to −53.86 kcal/mol) and VIE (7.0-7.4 eV) findings suggest that superhalogens-doped sulflower complexes are thermodynamically stable and show durable interaction among sulflower and doped superhalogens. Superhalogens doping on sulflower effectively shorten the energy gap from 4.46 eV (pure sulflower) to 4.17 eV in CaCl3@SF-5M isomer. Superhalogens doping causes a change in the dipole moment from 0 D of pure sulflower to 12.57 D in the CaCl3@SF-5M isomer. Proficient intermolecular charge transfers between sulflower and doped superhalogens were established by NCI and NBO analyses. UV-Vis investigation revealed that all superhalogen-doped sulflower complexes are adequately transparent in the near-infrared and visible wavelength ranges. Augmentation in polarizability value from 333.86 a.u.−569.98 a.u and in first hyperpolarizability from 0.00 a.u to 6.6 × 104 a.u. is achieved upon superhalogens doping. A striking NLO response (β0 = 6.6 × 104 a.u) is exhibited by CaCl3@SF-5M isomer. This report provides an efficient superhalogens doping technique for creating highly effective future NLO systems and recommends superhalogens-doped sulflower complexes as ideal entrants for future NLO applications. [ABSTRACT FROM AUTHOR]

The invention discloses a preparation method for nickel (II) nitrate hexahydrate boric acid and the growth of single crystals by the slow evaporation solution growth technique. Single crystal x-ray diffraction (XRD) analysis shows N2NHB crystallize in triclinic P crystal system with lattice parameters of a = 6.61 Å, b = 7.05 Å, c = 7.07 Å, α = 119.61°, β = 92.25°, γ = 101.11° and volume = 278 Å3. The chemical composition and the corresponding functional groups of the grown crystal have been identified by EDAX and FTIR analyses. Scanning electron microscope (SEM) pictograph indicated that the particles were closely spherical in shape with slight agglomeration. UV–Visible studies shows N2NHB crystal exhibit lower cut-off wavelength of 314 nm, wide optical window (320 – 800 nm) and wide band gap of 4.16 eV. According to the fluorescence spectrum, the emission occurs at a wavelength of 533 nm. Different temperatures were used to study the Grown crystalc dielectric behaviour. A positive photocurrent is found in the Grown crystal, as shown by the photoconductivity analysis. The second harmonic generation (SHG) capability was demonstrated by the standard Kurtz and Perry powder method. Open aperture Z-scan technique reveals that the material exhibits two-photon absorption phenomenon with nonlinear absorption coefficient of 0.75 × 10−11 m/W. The material displays optical limiting behaviour with an onset limiting threshold of 4.72 × 1012 W/m2. Altogether the grown N2NHB crystal can be utilized wide variety of optoelectronic applications of which optical limiting activity for laser safety devices is notable. [ABSTRACT FROM AUTHOR]

Purpose: The vibration problem of nonlinear structures is very challenging, especially for random excitations. Methods: This paper investigates the power spectral characteristics of the random vibration response of a structure with a nonlinear energy sink (NES) in the frequency domain. Using the statistical characteristics of system response, an optimized objective function is constructed, and a stochastic optimization method is established to realize the parameter optimization of the NES attachment of the structure under random excitation. The random excitation is modeled as a complex exponential series represented by random variables, and the multi-harmonic balance method (MHBM) is used to analyze the random vibration of the multi-degree-of-freedom (MDOF) coupled nonlinear system. Results: By introducing the alternating frequency time (AFT) approach, the analytical derivation of nonlinear constitutive equations in the frequency domain is avoided, and the iterative calculation of power spectral density (PSD) analysis of random vibration based on the frequency domain is effectively realized. Moreover, the peak shift and multi-peak response of the response PSD of the system coupled with NES are discussed. To solve the nonlinear optimization problem of NES system parameters, an MHBM–GA optimization approach is proposed, which realizes the parameter optimization of the nonlinear coupled system under random excitation. Conclusions: This study provides a new method for the vibration analysis and optimization design of NES under random excitation. [ABSTRACT FROM AUTHOR]

Conventional time-of-flight (TOF) measurements yield charge carrier mobilities in photovoltaic cells with time resolution limited by the RC time constant of the device, which is on the order of 0.1–1 µs for the systems targeted in the present work. We have recently developed an alternate TOF method, termed nonlinear photocurrent spectroscopy (NLPC), in which carrier drift velocities are determined with picosecond time resolution by applying a pair of laser pulses to a device with an experimentally controlled delay time. In this technique, carriers photoexcited by the first laser pulse are "probed" by way of recombination processes involving carriers associated with the second laser pulse. Here, we report NLPC measurements conducted with a simplified experimental apparatus in which synchronized 40 ps diode lasers enable delay times up to 100 µs at 5 kHz repetition rates. Carrier mobilities of ∼0.025 cm2/V/s are determined for MAPbI3 photovoltaic cells with active layer thicknesses of 240 and 460 nm using this instrument. Our experiments and model calculations suggest that the nonlinear response of the photocurrent weakens as the carrier densities photoexcited by the first laser pulse trap and broaden while traversing the active layer of a device. Based on this aspect of the signal generation mechanism, experiments conducted with co-propagating and counter-propagating laser beam geometries are leveraged to determine a 60 nm length scale of drift velocity dispersion in MAPbI3 films. Contributions from localized states induced by thermal fluctuations are consistent with drift velocity dispersion on this length scale. [ABSTRACT FROM AUTHOR]

We present a methodology for simulating multidimensional electronic spectra of molecular aggregates with coupling of electronic excitation to a structured environment using the stochastic non-Markovian quantum state diffusion (NMQSD) method in combination with perturbation theory for the response functions. A crucial aspect of our approach is that we propagate the NMQSD equation in a doubled system Hilbert space but with the same noise. We demonstrate that our approach shows fast convergence with respect to the number of stochastic trajectories, providing a promising technique for numerical calculation of two-dimensional electronic spectra of large molecular aggregates. [ABSTRACT FROM AUTHOR]

The electronic structure of the N3/TiO2 interface can directly influence the performance of a dye sensitized solar cell (DSSC). Therefore, it is crucial to understand the parameters that control the dye's orientation on the semiconductor's surface. A typical step in DSSC fabrication is to submerge the nanoparticulate semiconductor film in a solution containing the dye, the sensitizing solution. The pH of the N3 sensitizing solution determines the distribution of the N3 protonation states that exist in solution. Altering the pH of the sensitizing solution changes the N3 protonation states that exist in solution and, subsequently, the N3 protonation states that anchor to the TiO2 substrate. We utilize the surface specific technique of heterodyne detected vibrational sum frequency generation spectroscopy to determine the binding geometry of N3 on a TiO2 surface as a function of the sensitizing solution pH conditions. It is determined that significant reorientation of the dye occurs in pH ≤ 2.0 conditions due to the lack of N3-dye carboxylate anchoring groups participating in adsorption to the TiO2 substrate. Consequently, the change in molecular geometry is met with a change in the interfacial electronic structure that can hinder electron transfer in DSSC architectures. [ABSTRACT FROM AUTHOR]

Polar molecular crystals, with their densely stacked polar nonlinear optical (NLO) active units, are favored for their large second harmonic generation (SHG) responses and birefringence. However, their potential for practical applications as Infrared (IR) NLO materials has historically been underappreciated due to the weak inter‐molecular interaction forces that may compromise their physicochemical properties. In this study, we propose molecular crystals with polar molecular cages as a treasure‐house for the development of superior IR NLO materials and a representative system, binary chalcogenide molecular crystals, composed of [P4Sn] (n=3–9) polar molecular cages, is introduced. These crystals may not only achieve wide band gap, large SHG response, and birefringence in a single structure, but also exhibit favorable physicochemical properties. We subsequently obtained a polar molecular crystal, α‐P4S5, which demonstrated exceptional IR optical properties, including a strong SHG response (1.1×AGS), wide band gap (3.02 eV), large birefringence (0.134@2050 nm), and a broad transmission range (0.41–14.7 μm). Moreover, it showed excellent water resistance and hardness. These findings highlight the potential of polar molecular crystals as a promising platform for the development of high‐performance IR NLO materials. [ABSTRACT FROM AUTHOR]

Making oppositely charged metal‐organic cages (MOCs) into a tightly ordered structure may bring interesting functions. Herein, we report a novel structure composed of anionic (Zr4L6)8− (L=embonate) tetrahedral cages and in situ‐formed cationic [Zn4(Bim)4]4+ (Bim=[BH(im)3]−; im=imidazole) cubic cages. Chiral transfer is observed from enantiopure (Zr4L6)8− cage to enantiopure [Zn4(Bim)4]4+ cage. A pair of enantiomers (PTC‐373(Δ) and PTC‐373(Λ)) are formed. PTC‐373 exhibits high chemical and thermal stabilities, affording an interesting single‐crystal‐to‐single‐crystal transformation. More importantly, the combination of ionic pair cages significantly enhances its third‐order nonlinear optical property, and its thin‐film exhibits an excellent optical limiting effect. [ABSTRACT FROM AUTHOR]

Carbon family elements (Si, Ge, Sn, Pb) have attracted a lot of attention because of their unique structural features and potential applications in microelectronics industry. Here, the structure, chemical stability, electronic properties, and nonlinear optical properties of neutral and charged Au@X20H20 (X=Si, Ge, Sn, Pb) clusters have been systematically studied using density‐functional theory calculations. Structurally, the neutral/anionic Au@X20H20 (X=Si, Ge, Sn) as well as cationic Au@Pb20H20 possess Au‐endohedral (XH)20 unit, forming fullerene‐like framework, whereas other species are Au‐doped structures with hydrogen‐bridged bond. Analysis of binding energy and HOMO‐LUMO energy gaps reveals that the charged clusters possess high chemical stabilities due to closed‐shell structures. The charge transfers from X20 cage to Au atom, and the Au atom acts as electron acceptor. The Au atom and charged states play an important role in the structural stability, and can effectively modulate the electronic properties of clusters. Interestingly, the neutral Au@X20H20 (X=Si, Sn) clusters possess large first hyperpolarizabilities, especially for Au@Sn20H20, which has remarkably giant value (~5.65×108 a. u.), and the enhanced NLO behaviors can be further explained by the TDDFT calculation. The work may provide a theoretical reference for further applications considered as novel cluster‐assembled nanomaterials. [ABSTRACT FROM AUTHOR]

Crystal–liquid–glass, which combines the tunable properties of crystalline compounds with the processability of glasses, has emerged as a new class of materials for fabricating bulk‐shapable devices in real applications. Inspired by the characteristics of deep eutectic solvent (DES) mixtures involving significant depressions in melting points compared to their neat constituent components, in this study, we designed and synthesized the first examples of meltable aluminum oxo clusters (AlOCs) via lattice doping with DESs at the molecular level. The abundant and strong hydrogen bonding between the aluminum molecular ring, DES components, and lattice solvents is postulated to be the root that affords melting point depressions and, thus, "melting" clusters. We prepared a transparent bubble‐free glass film under autogenous pressure using a hot‐press method. These cluster‐based films exhibited luminescent and nonlinear optical properties similar to those of pristine crystalline compounds. Our study belongs to the interdisciplinary disciplines of chemistry and physics. It not only breaks the limitations of crystalline glass on metal and ligand types but also acts as a general guide for extending the range of meltable crystalline materials. [ABSTRACT FROM AUTHOR]

Based on density functional theory (DFT) and wave function analysis, the ultraviolet and visible spectrophotometry (UV-Vis) spectra and Raman spectra of 1-meso and 1-rac obtained by the chiral separation of chiral nanographenes are theoretically investigated. The electron excitation properties of 1-meso and 1-rac are studied by means of transition density matrix (TDM) and charge density difference (CDD) diagrams. The intermolecular interaction is discussed based on an independent gradient model based on Hirshfeld partition (IGMH). The interaction of 1-meso and 1-rac with the external environment is studied using the electrostatic potential (ESP), and the electron delocalization degree of 1-meso and 1-rac is studied based on the magnetically induced current under the external magnetic field. Through the chiral separation of 1-rac, two enantiomers, 1-(P, P) and 1-(M, M), were obtained. The electrical–magnetic interaction of the molecule is revealed by analyzing the electron circular dichroism (ECD) spectra of 1-meso, 1-(P, P) and 1-(M, M), the transition electric dipole moment (TEDM) and the transition magnetic dipole moment (TMDM). It is found that 1-(P, P) and 1-(M, M) have opposite chiral properties due to the inversion of the structure. [ABSTRACT FROM AUTHOR]

This paper addresses an important method for finding traveling wave solutions of nonlinear partial differential equations, solutions that correspond to a specific symmetry reduction of the equations. The method is known as the simplest equation method and it is usually applied with two a priori choices: a power series in which solutions are sought and a predefined auxiliary equation. Uninspired choices can block the solving process. We propose a procedure that allows for the establishment of their optimal forms, compatible with the nonlinear equation to be solved. The procedure will be illustrated on the rather large class of reaction–diffusion equations, with examples of two of its subclasses: those containing the Chafee–Infante and Dodd–Bullough–Mikhailov models, respectively. We will see that Riccati is the optimal auxiliary equation for solving the first model, while it cannot directly solve the second. The elliptic Jacobi equation represents the most natural and suitable choice in this second case. [ABSTRACT FROM AUTHOR]

A new complex formed from the reaction of benzene-1,2,4,5-tetracarboxylic dianhydride with zinc(II) acetate dihydrate was synthesized and characterized by single-crystal X-ray diffraction, thermal analysis (TGA), and density functional theory (DFT). [C10H4O8][Zn(H2O)6] (1), crystallized in a monoclinic system with space group P2/m. Theoretical modeling was performed at the DFT/B3LYP computational level with 6–311 G(d,p) and LanL2DZ basis sets. The Zn(II) is six-coordinate, forming an ideal octahedral geometry. A Hirshfeld surface analysis of the complex indicated that H···O/O···H contacts contribute to 47.8% of the crystal packing. The stability of 1 was investigated by determining the global chemical reactivity descriptors (GCRD). The nonlinear optical (NLO) behavior was investigated by analyzing the dipole moment, polarizability, and first-order hyperpolarizability (μ, α and β) via a theoretical approach, indicating that 1 has important nonlinear optical properties. A molecular docking study shows binding of 1 on the active site of receptors from human cyclooxygenase-2 enzyme (PDB code: 5IKT) and Escherichia coli MenB (PDB code: 3T88). [ABSTRACT FROM AUTHOR]

The present work intended to report the synthesis of newly designed donor-acceptor complexes of the pyrimidine-based system namely TAPHIA 1 and TAPHIA 2, which are symphonized to give the NLO properties. The methodologies adopted for both complexes were different and hence influenced their geometrical properties. The synthesized complexes were characterized using different techniques including SCXRD, FTIR, UV, PXRD, and TGA to confirm their formation. The SCXRD analysis revealed that TAPHIA 1 was crystallized in the Pca21 space group in an orthorhombic system while TAPHIA 2 was crystallized in the P21/c space group in a monoclinic system. The third-order NLO properties of both complexes were explored using the Z-Scan technique by employing a continuous wave (CW) diode laser of 520 nm. The third-order NLO parameters including nonlinear refractive index (n2), nonlinear absorption coefficient (β) and nonlinear optical susceptibility (χ (3)) were calculated at different powers; 40, 50 and 60 mW at fixed solution concentration (10 mM) for both the complexes. Moreover, the experimental properties including NLO, FTIR, and UV were well corroborated with theoretical results obtained at the B3LYP-D3/6-31++G(d,p) level of theory. The analysis of the theoretical and experimental properties of both complexes suggests that TAPHIA 2 is a better applicant to be employed in optical devices than TAPHIA 1 due to the enhanced ability of internal charge transfer. Symphonizing effect of NLO properties exhibited by two newly synthesized donor acceptor complexes namely TAPHIA 1 and TAPHIA 2. The NLO potential of the two newly reported organic complexes were influenced by their structural properties and charge transfer ability, made them good applicants to be employed in optoelectronic field. [ABSTRACT FROM AUTHOR]