Nonlinear Optical Properties Research Articles

The influence of spin-orbit coupling on the electronic structure and optical properties of α-BiB3O6 crystals: a first-principles investigation

The α-BiB3O6 (BIBO) crystal is highly regarded in the field of nonlinear optical (NLO) due to its excellent ultraviolet (UV) NLO properties, including a short ultraviolet cutoff edge (270 nm), appropriate birefringence (Δn = 0.175@546 nm), and strong second harmonic generation (deff = 3.20 pm V−1). In this study, the first-principles computational software PWmat was employed to conduct theoretical calculations on BIBO crystals, including the non-negligible spin-orbit coupling (SOC) effects induced by the presence of the heavy element bismuth (Bi). The results show that after the inclusion of the SOC, the calculated birefringence (0.173@546 nm) and effective second harmonic generation (SHG) coefficient (deff = 3.16 pm V−1) are in good agreement with experimental data. Furthermore, comparative analysis has demonstrated that the changes in the band structure induced by the SOC effect are significant factors influencing the optical properties of the material.

Study on UV-VIS characteristics of Aluminum Zinc Oxide nanoparticles through manganese substitution using Wemple-Di domenico method and diffuse reflectance spectroscopy

In this research Manganese-substitution impact on linear and nonlinear (NL) optical properties of Aluminum-doped ZnO (AlZnO) Nanoparticles (NPs) are investigated. Utilizing measured data of reflectance acquired from the DRS, the higher-order NL optical characteristics of the provided NPs are examined. The maximum quantity of NL susceptibility χ3 is measured to be around 3.945 × 10−10 esu at wavelength λ = 520 nm and 7.467 × 10−11 esu at wavelength λ = 530 nm for AlZnO and Manganese-substituted Aluminum-doped Zinc-Oxide (Mn-also) NPs, for particle sizes 14−67 nm and 11−54 nm, consecutively. Consequently, the synthesis method (sol–gel) which is used in this work concluded a decrease in particle size and different optical behavior especially in UV spectral regions during the substitution with Manganese in comparison with the AlZnO. This decrement assures that a decrease in the size of crystallite induces a decline in the χ3. The obtained optical parameters are red shifted with the Manganese substitution. Also, the NL absorption coefficient (β c(m/W)) is enhanced in the UV range. The maximum of the NL absorption coefficient (β c(m/W)), for AlZnO and Mn-AlZnO NPs, are determined (at λ = 250 nm) 2.24 × 10−18 (m/W) and 5.76 × 10−15 (m/W) respectively.

Optical nonlinear properties of a new polyamide from crystal violet terephthalate

In this study, the nonlinear optical properties of a new polymer poly crystal violet terephthalate (PCVT) as a solution and a thin film with different concentrations of 0.2, 0.6, and 1 mM and input power were investigated by using Z-scan technique at 532 nm CW laser beam wavelength. The negative nonlinear refractive index n 2 as well as reverse saturable and saturable absorption β of the solution and film PCVT samples were determined. Figures of merit were also determined. In comparison with the Z-scan results, a self-diffraction pattern setup was used to measure nonlinear refractive index. Results showed a significant laser power dependence of the number of far-field diffraction rings with power and concentration, consistent with the Z-scan data. The PCVT sample exhibited good optical limiting behavior. Hence, PCVT has important nonlinear properties, and its figures of merit can be optimized by adjusting the PCVT concentration and input power. PCVT is a promising candidate for the design of optical photonic switching and optical limiter devices.

NLOphoric unsymmetrically substituted D-π-A benzodifuranone dyes: Density functional theory, time dependent-density functional theory, and non-linear optical studies

The linear and non-linear optical properties of thirty-five unsymmetrically substituted compounds are studied using density functional theory and time-dependent density functional theory methods (B3LYP/6311++G(d,p), CAM-B3LYP/6311++G(d,p) and M06-2X/6311++G(d,p)). A comparable set of functionals is also used to investigate vertical excitation. It is observed that the inclusion of the nitrogen-substituted electron-donating group along with the electron-withdrawing group led to more red-shifted absorption maxima and exhibited an excellent (non-linear optical) NLO response. The geometrical framework, dipole moment, and other descriptors, HOMO-LUMO energy gaps, linear polarizability, first-order and second-order hyperpolarizability are calculated to investigate the effect of different electron donating and accepting substituents on the NLO properties of benzodifuranone chromophores. In cases where nitrogen substituents are added, the electron density is more widely spread throughout the donor in HOMO and more displaced to the acceptor in LUMO. The computed first-order and second-order hyperpolarizability values and decreasing HOMO-LUMO energy gaps in disubstituted nitrogen-containing compounds show that 1a-1e, 4a-4e, 5a-5e are promising candidates in all functionals for better NLO properties.

Optical sensing and nonlinear optical properties of Cr-doped MoO3/PEDOT:PSS Nanocomposites

In this study, we observed a negative UV photoresponse that switched to a positive photoresponse in Cr-doped MoO3/PEDOT:PSS nanocomposite films(NCF) prepared via drop-casting. MoO3 and Cr-doped MoO3 were synthesized using a hot oil bath co-precipitation method, combined with PEDOT:PSS (poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate)), and coated onto flexible OHP sheets. The open aperture z-scan method investigated the nonlinear optical properties of NCF on the glass substrate. The films were characterized by X-ray diffraction, scanning electron microscopic (SEM), UV–Vis spectroscopy, and Fourier Transformed Infrared (FTIR). Chromium doping caused minor changes in lattice parameters, crystalline size, and microstrain. UV spectroscopy revealed an increase in bandgap with higher Cr–MoO3 concentrations. The photoresponse of different Cr–MoO3 concentrations showed an initial current decrease under UV light, but the photoresponse became positive beyond a threshold and continued to improve. Nonlinear optical studies indicated saturable absorption in the nanocomposite. This work enhances our understanding of Cr-doped MoO3/PEDOT:PSS nanocomposites, contributing to advancements in flexible UV photodetectors and nonlinear optical applications.

First principles investigations of linear and nonlinear optical, radiation shielding and thermoelectric properties of the non-centrosymmetric Ba-based chalcogenides Ba2In2X5 (X=S, Te)

We explore the structural, elastic, optoelectronic, Radiation Shielding, and thermoelectric properties of Ba2In2X5 (X = S, Te) using first-principles computations and semi-classical Boltzmann Transport equations. These materials are classified as semiconductors exhibiting band gaps of 2.0 eV and 3.0 eV for both investigated NLO compounds that have more significant direct band gaps of superior optical birefringence and second-order NLO coefficients. The bonding properties have been investigated by analyzing the electron charge density (ECD) contour of the (1 0 1) crystallographic plane. It is clear from the reflectivity spectra that both compounds have a high degree of reflectivity, which could make them useful as UV and visible light shields. From 0 to 14.0 eV, the approximated reflectivity values, R (ω), are displayed against the incident photon energy. Therefore, the reflectivity is around 30 % before E ≈ 12.0 eV and 40 % reflection at ∼13.0 eV. Phase matching is possible for both compounds detected, as shown by the birefringence computations. Furthermore, the radiation shielding properties of Ba2In2S5 and Ba2In2Te5 have been evaluated using Phy-X software, demonstrating their potential effectiveness in medical and nuclear energy applications. The thermoelectric properties display N-type nature at low temperatures when the Seebeck coefficient changes from N to P-type at higher temperature ranges. These compounds have remarkable optical and thermal properties, rendering them highly attractive materials for thermoelectric and optoelectronic devices.

Non-linear optical properties of hybrid materials of (OLi3) superalkali doped perylene diimide (PDI) derivative: comprehensively study via silico-technique

PDI-Imidazole and PDI-Imidazole combined with OLi3 (OLi3@PDI-Imidazole) were the two types of materials that we examined in this study to see how light behaved in each of the complex. To explore this, we employed the three different method such as rB3LYP/6–31G(d, p) DFT, CAM-B3LYP and WB97XD. The impact of PDI-Imidazole and OLi3@PDI-Imidazole geometries, maximum absorption ( λmax ), FMO, vertical ionization energies ( EVI ), Binding Energies ( Eb ), Hyperpolarizabilities, DOS, Dipole Moments (μ), ESP, EDDM, and Global Reactivity parameters have been examined. The type of contacts as well as the vibrational frequencies of PDI-Imidazole and OLi3@PDI-Imidazole were investigated using NCl, iso-surface, Raman spectroscopy, and IR research. The electron transport characteristics of the OLi3@PDI-Imidazole surface was significantly enhanced in comparison to the PDI-Imidazole surface by lowering the bandgap energies from 1.27 eV to 1.03 eV. In contrast to the pure PDI-Imidazole surface, which had lower values for linear polarizability ( α0 ) (547.08 au) and first hyperpolarizability ( β0 )(201.133au), OLi3@PDI-Imidazole surface displayed significant enhancements in linear polarizability ( α0 = 706.472 au) and first hyperpolarizability ( β0 = 21314.360 au). It was observed by TD-DFT calculations that all the compounds had appreciable improvements in their interaction energies, HOMO–LUMO and UV–vis absorption and vertical ionization potential. Future development of nonlinear optical (NLO) devices has been discovered to benefit from the addition of OLi3 to the PDI-Imidazole surface.

Synthesis, photophysical properties, and in-silico nonlinear optics of 3-hydroxy-N-phenyl-2-naphthamide and its acetate, acrylate, and benzoate derivative

In this study, we report the successful growth of single crystals of 3-hydroxynaphthalene-2-carboxanilides (NAS) with a monoclinic structure in the P21/c space group and space group number of 14 for the first time. We have developed a yield and time-effective modified synthetic procedure using a synthetic reactor by replacing the traditional microwave method. Additionally, acylated derivatives of NAS, including novel acryloyl derivative (NAS AC), are synthesized with a modified procedure, replacing pyridine with triethylamine.We investigate the structural, photophysical, and quantum chemical properties of N-(4-acetylphenyl)-2-oxo-2H-chromene-3-carboxamide (NAS) and its acylated derivatives (NAS AC, NAS ACT, NAS BZ). Photophysical studies reveal significant Stokes shifts observed in different solvents, including time-enhanced fluorescence in DMSO, attributed to solvent relaxation processes. Natural bond orbital (NBO) analysis, molecular electrostatic potential (MEP) maps, and frontier molecular orbital (FMO) provide insights into electronic interactions and asymmetric charge distribution. Low-lying LUMO values of these compounds (-2.31 eV to -1.95 eV) support candidature for the electron acceptor applications. Nonlinear optical properties were thoroughly investigated, with NAS displaying the highest static first-order hyperpolarizability (17.89 × 10−30 esu) and NAS BZ exhibiting the highest second-order hyperpolarizability (113.09 × 10−36 esu), indicating significant nonlinear optical responses. Thermal stability (TGA and DTA) highlights the significant range of temperatures for the NLO applications.

Growth, characterization and cognition of 2-cyanopyridinium perchlorate single crystals for nonlinear optical applications.

The fascinating electronic applications attracted researchers to explore the field of nonlinear optical (NLO) materials. The slow evaporation of solvent technique (SEST) was employed to grow the 2-cyanopyridinium perchlorate (2-CPPC) NLO single crystals. The cell parameters of the grown 2-CPPC crystal are confirmed by the single crystal X-ray diffraction (SCXRD) study. The powder X-ray diffraction studies confirm the crystallinity of 2-CPPC crystals, and the peaks were indexed. The computation for the geometry optimization, HOMO-LUMO energy gap, global reactivity parameters, natural bond orbital (NBO) analysis, polarizability, and hyperpolarizability of the 2-CPPC molecule was done using B3LYP (6-311G basis set) functional of DFT method. The experimental FTIR and UV-Vis results of the 2-CPPC compound were compared with the simulated results. The second harmonic generation (SHG) study for the 2-CPPC crystal was employed using Kurtz-Perry powder technique. Single beam Z-scan technique using He-Ne laser is used to study the third-order NLO properties.

Linear and Nonlinear Optical Properties of Symmetric and Asymmetric Double Triangular Quantum Dots Withinside the Presence of Magnetic Field

AbstractLinear and third‐order nonlinear optical absorption coefficients and relative refractive index changes in symmetric and asymmetric double triangular quantum dots are examined theoretically. The dependence of these optical properties on the magnetic field is examined. After calculating energies and wave functions within the effective mass and parabolic band approaches, analytical expressions of linear and nonlinear optical properties are obtained using the compact density matrix approach and iterative method. Numerical calculations are presented for typical GaAs/AlGaAs material. The results show that the magnetic field causes different effects on the and transitions. Moreover, the calculated results also reveal that the resonance frequency and nonlinear contribution are different in symmetric and asymmetric structures. As a result, it is concluded that the magnetic field plays a vital and important role in the electronic and optical properties of the system and can be used to tune the inter‐subband transitions and change the corresponding optical sensitivities.

Multifunctional Organometallic Compounds: An Interesting Luminescent NLO‐active Alkynylplatinum(II) Complex

Reaction of 4‐methylphenylacetylide with the known chlorido platinum(II) complex bearing the cyclometalated 1,3‐bis(pyridin‐2‐yl)‐4,6‐difluoro‐benzene ligand afforded a novel alkynyl platinum(II) complex, 1, that was fully characterized by elemental analysis, NMR and UV‐visible spectroscopies, and by photoluminescence measurements. Its structure was determined by X‐ray diffraction studies on a single crystal whereas its second‐order nonlinear optical (NLO) properties were determined in solution by the Electric‐Field Induced Second Harmonic generation method. The novel multifunctional complex 1 is characterized by good luminescence properties, like the related chlorido Pt(II) complex, but by a much higher second‐order NLO response.

Magnetic field-engineered optical nonlinearity in germanene nanotubes

Abstract The linear and nonlinear optical properties of germanene nanotubes (GeNTs) under the influence of magnetic fields are investigated through theoretical analysis. By employing a tight-binding model beyond the Dirac cone approximation, the electronic band structure, density of states, dipole matrix elements, and third-order nonlinear optical susceptibilities are calculated. The application of a magnetic field induces a Zeeman splitting of the energy levels, breaking the band degeneracy. Consequently, the dipole matrix elements exhibit a magnetic field dependence, altering the intensity and number of allowed transitions. In the infrared and ultraviolet energy regions, the linear optical absorption spectrum displays the splitting of peaks into dual neighboring peaks, with the splitting distance linearly dependent on the magnetic field strength. The third-order nonlinear optical susceptibilities, χTHG(3)3ω and χIDIR(3)ω, reveal the emergence of multiple resonance peaks in different energy regions due to two-photon and three-photon absorption processes. The magnetic field significantly influences the number, position, and height of these optical peaks, enabling effective control over the nonlinear optical response. By investigating the scaled energy (E/E_g) dependence, a universal behavior is observed for the three- and two photon resonance peaks, where their positions remain constant, but their peak intensities are significantly enhanced under the influence of the magnetic field. These findings demonstrate the potential of GeNTs as tunable nonlinear optical materials, with the magnetic field serving as an effective parameter for engineering their optical properties for various applications in optoelectronics, photonics, and related fields.

Exploring the impact of thin film thicknesses on the linear and nonlinear optical properties of ZrO2 thin film

Exploring the impact of thin film thicknesses on the linear and nonlinear optical properties of ZrO2 thin film

Small compressive strain tuning of α-TeO2 and β-TeO2 polymorphs: Electronic, linear, and nonlinear optical properties from first-principles calculations

This study examines the effects of 2 % compressive strain on the structural, electronic, and optical properties of α-TeO2 and β-TeO2 polymorphs. α-TeO2’s bandgap increases from 3.64 eV to 3.70 eV, while β-TeO2’s decreases from 3.632 to 3.53 eV. Lattice parameters uniformly reduce in α-TeO2, but vary dissimilarly in β-TeO2. PDOS analysis shows O-2p and Te-5p states dominate near the band edges. Optical behavior is anisotropic, with enhanced polarizability and refractive indices under strain. Nonlinear optical properties improve with increased strain, especially the non-linear susceptibility components, which are relevant for second-harmonic generation. Born Effective Charges show increased Te polarization and reduced oxygen polarization, impacting dielectric response.

Theoretical exploration of binary mixtures derived from hydrogen bond liquid crystalline soft materials for optical device fabrication

Binary mixtures are obtained from 4-Nitrobenzaldehyde (NBA), 4-(heptyloxy)benzoic acid (7OBA) and 4-(octyloxy)benzoic acid (8OBA) abbreviated as NBA + 7OBA and NBA + 8OBA. Density Functional Theory (DFT) is used to optimize the resultant molecular structures. HOMO–LUMO and NBO analysis are adapted in obtaining the charge transfer phenomenon of the binaries. Molecular electrostatic Potential (MEP) analysis reveals the active sites of liquid crystals. Atomic charge distribution of the binary mixture is investigated theoretically. Topological analysis is carried out to understand the intermolecular interaction between non mesogenic NBA and mesogenic precursors along with nonlinear optical properties. The results obtained are correlated with the experimental data obtained.

Solid-Solution MXenes: Synthesis, Properties, and Applications.

ConspectusMXenes, among other two-dimensional (2D) materials such as graphene, hexagonal BN, transition metal dichalcogenides (TMDs), 2D metal-organic frameworks (MOFs), and covalent organic frameworks (COFs), are the fastest growing class discovered thus far. The general formula of MXenes is Mn+1XnTx, where M, X, and Tx represent an early transition metal (Ti, V, Nb, Mo, etc.), C and/or N, and the surface functional groups (typically, O, OH, F, Cl), respectively, and n can be between 1 and 4. MXenes as a class of materials have extraordinary properties, such as high electrical conductivity, nonlinear optical properties, solution processability, scalability and ease of synthesis, redox capability, and tunable surface properties, among others; the specific properties, however, depend on their chemistry. Since the initial report of the first MXene in 2011, the research community has primarily focused on Ti3C2Tx, and the amount of research work to investigate its synthesis and properties has increased exponentially over the years. In materials science, alloying is a useful way of synthesizing new materials to improve the properties of a class of materials. Advancement of steel and synthesis of inorganic semiconductors can be regarded as some of the major historical advancements in the concept of alloying. Thus, just one year after the initial report of MXenes, the first solid-solution MXene, (TiNb)2CTx, was reported, which demonstrates the inherent chemical tunability of this class of materials.MXenes have two sites for compositional variation: elemental substitution on both the metal (M) and carbon/nitrogen (X) sites, presenting promising routes for tailoring their properties. X-site solid-solutions include carbonitride MXenes and are the least studied class of MXenes to date. Comparatively, multi-M MXenes have acquired significant attention, leading to the extreme example of high-entropy solid-solution MXenes. By using multiple M elements, a significant expansion of the structural and chemical diversity is possible, giving rise to novel chemical, magnetic, electronic, and optical properties that cannot be accessed by single-M MXenes. Solid-solution MXenes represent the largest and most tunable class of MXenes; solid-solution MXenes are those that have multiple metals that are randomly distributed on their M sites with no distinct chemical ordering. Using multiple M elements in MXenes, it is possible to synthesize novel MXene structures that cannot be produced otherwise, such as M5X4Tx MXenes. Based on their chemistry, it is possible to rationally control the electronic, optical, mechanical, and chemical properties in a way that no other class of MXenes can. In some cases, the resultant property is linearly related to the chemistry, such as the electrical conductivity, while in other cases the properties are nonlinear or emergent: optical properties, enabling these MXenes to fulfill roles that no other MXene, or 2D material, can.In this Account, we discuss the recent progress in the synthesis, properties, applications, and outlook of solid-solution MXenes. Importantly, we demonstrate how multi-M solid-solutions can be used to tailor properties for specific applications easily.

Investigation of synthesis, spectroscopic characterization, crystal structure, and computational studies of 3-(4-(dimethylamino)phenyl)-1,5-di(thiophen-2- yl)pentane-1,5-dione as potent against Cathepsin S

The chief purpose of this work was to synthesize and characterize 3-(4-(dimethylamino)phenyl)-1,5-di(thiophen-2-yl)pentane-1,5-dione (4) whose structure was subsequently confirmed by single-crystal X-ray analysis. This molecule adopts a conformation approximating a three-bladed fan. In the crystal, C–H···O and C–H···S hydrogen bonds, together with C–H···π(ring) interactions form corrugated layers parallel to the bc plane. Electronic structure calculations were performed at the ωB97xd/def2tzvp level to explore the reactivity and topology of the molecule. Quantum theory of atoms in molecule (QTAIM) and NBO studies provide bonding characteristics and the extent of charge transfer with orbital energies computed from FMO theory together with optical and nonlinear optical (NLO) properties. A Hirschfeld surface analysis was performed to explore the nature of interactions in the crystal packing and the dispersion interactions were found to have a significant role in stabilizing the crystal structure. The H···H interactions are the most significant among the intermolecular interactions. Compound 4 was subjected to structural activity relationship analysis and exhibited potency against Cathepsin S. Molecular docking and molecular dynamics analysis were carried out to understand the binding interaction mechanism and stability of 4 in its complex with Cathepsin S.

Investigations on the growth, spectral, optical, electrical, thermal and nonlinear optical properties of L-valine itaconic acid single crystal

A nonlinear optical single crystal of L-Valine Itaconic Acid (LVIA) was grown at room temperature from an aqueous solution by using the slow evaporation method. The grown crystal was undergone X-ray diffraction investigation, which confirm that the crystal belongs to orthorhombic system with the non-centro symmetric Pbca space group. This single crystal contains several functional groups, according to FTIR spectroscopic analysis there were identified. By analyzing the crystal's UV–visible spectrum, based on its optical transparency this crystal may use for optoelectronic device manufacturing. The emission happens at 553 nm wavelength, according to the photoluminescence spectrum. Thermo gravimetric and differential thermal analytical studies helps us to measure title crystal melting point and thermal stability. At various temperatures, the dielectric property of the crystal was found out. The Kurtz-powder method has been used to study the phenomenon of Second Harmonic Generation (SHG) in the crystal.

Ternary Boron Carbon Nitride nanosheets with improved and controllable linear and nonlinear optical response for efficient photocatalytic performance

This work reports the systematic variation of linear and nonlinear optical (NLO) properties of ternary boron carbon nitride (BCN) nanosheets with varying carbon concentrations. These nanosheets are synthesized by the thermal substitutional method to modulate the band-gap of BCN nanosheets by varying the hBN and graphene domain ratios which is confirmed through UV-Vis absorption spectroscopy. The third-order optical nonlinearity of nanosheets was explored through the Z-scan technique. With increases in both carbon content and laser power, samples' NLO properties have shifted from saturable absorption to reverse saturable absorption. The enhanced nonlinearity with carbon concentration in BCN samples was responsible for higher photoinduced charge separation time. In UV-Vis driven photoreduction of organic pollutants, BCN nanosheets with a decreased bandgap and an increased charge separation time show higher catalytic efficiency. Therefore, based on the combined effect of many processes, the results revealed that the BCN nanosheets displayed greater potential for photoinduced reduction.

Tuning the photophysical and NLO properties of β-diketonates derived from coumarin-triphenylamine-chalcones: effect of the BF2 group.

Herein the synthesis of three difluoroboron β-diketonate complexes (7a-c) and one chalcone (7d) with coumarin and triphenylamine fragments is described. The effect of the inclusion of the difluoroboron (BF2) group and a phenyl linker on the photophysical properties, intramolecular charge transfer (ICT) and nonlinear optical (NLO) properties was studied. These dyes exhibited excellent ICT properties due to their A-π-D and D-π-A-π-D type push-pull configuration. Thus, all compounds presented a strong solvatochromism, given the absorption and emission maxima shifted to red because of the increase in the polarity of the medium. In addition to this, 7a-d showed the formation of a twisted intramolecular charge transfer (TICT) state, which quenched fluorescence in polar solvents. Compounds 7a, 7b and 7d exhibited aggregation-induced emission (AIE) in MeCN/H2O mixtures, while 7c did not have this behavior. In addition, all compounds showed emission in the solid state. Using DFT and TD-DFT calculations, the molecular geometries of the ground state S0 and the first excited state S1 were elucidated, which confirmed the formation of a TICT state. Furthermore, the theoretical and experimental absorption electronic transitions were correlated by testing different functionals: B3LYP, CAM-B3LYP, PBE0, wB97XD, HSEH1PBE and M062X. Frontier molecular orbitals (FOMs) and molecular electrostatic potentials (MEPs) supported the ICT from the donor to the acceptor group. The global reactivity descriptors were studied and the NLO properties were predicted by calculating first (βtot) and second-order (γave) hyperpolarizabilities, revealing that 7a-d would present promising NLO behavior.