Showing papers on "Hyperpolarizability published in 2019"
TL;DR: In this article, the geometric structures, electronic properties, and nonlinear optical responses of graphdiyne (GDY) complexes with single adsorbed alkali metals (AM: Li, Na, K) were systematically investigated using density functional theory calculations.
Abstract: Novel two-dimensional (2D) materials with promising and tunable nonlinear optical (NLO) properties are desirable for the development of optoelectronic nanodevices. Here, the geometric structures, electronic properties, and nonlinear optical responses of graphene (GE), graphyne (GY), and graphdiyne (GDY) complexes with single adsorbed alkali metals (AM: Li, Na, K) were systematically investigated using density functional theory calculations. All the alkali metals are energetically preferred for interacting with the large triangular holes in extensively delocalized π-conjugated graphyne and graphdiyne via an intramolecular electron donor–acceptor (D-π-A) process and can be stabilized by van der Waals interactions. Moreover, AM@GY and AM@GDY (AM = Li, Na, K) exhibit dramatically higher structural stability than AM@GE owing to their high binding energies. The effects of doping alkali metal atoms into the surface of GDY on the electronic structures were investigated by an analysis of the HOMO–LUMO gap and density of states. The strong alkalide characteristics of these complexes can be demonstrated by their NBO charges and lower vertical ionization potentials (VIPs). In addition, the adsorption of alkali metals greatly increases the first hyperpolarizability (βtot), and AM@GDY possesses exceptionally high βtot values (8.57 × 104 to 3.93 × 105 a.u.) in comparison with AM@GE and AM@GY owing to its unique structural patterns. The frequency dependences of the electro-optical (EO) Pockels effect and second-harmonic generation (SHG) were analyzed in order to investigate the dynamic NLO process, and it was revealed that SHG resonance enhancement takes place at ω = 0.10 a.u. The present investigation not only highlights the importance of the adsorption of single alkali metals on the surface of GDY for enhancing its NLO properties but also indicates that AM@GDY complexes are potentially important materials for next-generation graphdiyne-based optoelectronics applications.
91 citations
TL;DR: In this article, a series of inorganic electrides (Li2F, Li3O and Li4N) are designed by doping of Al12P12 nanocluster with superalkalis and studied through density functional theory (DFT) for their geometrical, electronic and nonlinear optical properties.
89 citations
TL;DR: In this paper, the molecular structure of the title compound has been investigated using experimental (FT-IR, FT-Raman and NMR) and theoretical (DFT) techniques.
73 citations
TL;DR: The first hyperpolarizability which is an important parameter for future studies of nonlinear optics (NLO) was calculated to check the potential of the molecule to be an NLO material and a comparison of the physiochemical parameters of PIDAA and commercially available drugs was carried out.
68 citations
TL;DR: In this article, the effect of different superalkalis and different doping positions on the nonlinear optical response of B12P12 nanostructures was investigated using density functional theory (DFT).
Abstract: Three series of compounds Li2F@B12P12, Li3O@B12P12 and Li4N@B12P12 are theoretically designed and investigated for their nonlinear optical response using density functional theory (DFT). Computational results reveal that isomers VIII and X are inorganic electrides whereas the others are excess electron systems. Interaction energies reveal that these systems are quite stable and superalkalis are chemisorbed on the nanocage. Doping of a B12P12 nanocage with superalkali brings a considerable increase in the first hyperpolarizability response of the system. The highest first hyperpolarizability (β0 = 3.48 × 105 a.u.) along with good ultraviolet transparency is observed for isomer III of Li2F@B12P12. Moreover, all three series of compounds are systemically studied for the effect of different superalkalis and different doping positions on the nonlinear optical response. This study will be advantageous for promoting the potential applications of the fullerene-like superalkali doped B12P12 nanostructures in new types of electronic nanodevices and high-performance nonlinear optical materials with good ultraviolet transparency.
59 citations
TL;DR: In this article, the target compound, 2-amino-4- (4-nitrophenyl)−5,6-dihydrobenzo [h] quinoline-3-carbonitrile, has been synthesized and characterized by FT-IR, 1H-NMR, 13C- NMR, and X-Ray single crystal determination as experimental.
58 citations
TL;DR: In this paper, the structural, vibrational, electronic, non linear optical, biological and thermodynamic properties of the title compound were investigated using spectroscopic techniques like FT-IR and FT-Raman.
58 citations
TL;DR: Based on DFT calculations, a new series of superalkali doped graphdiyne (GDY) complexes, M2X@GDY (M = Li, Na, K and X = F, Cl, Br) having electron donor and acceptor (D-π-A) framework was designed in this paper.
58 citations
TL;DR: In this article, the effect of doping different superalkalis (Li3O, Na3O and K3O) over Zn12O12 nanocages is also studied.
Abstract: Fabrication of stable nonlinear optical materials is highly demanding due to their widespread applications in optical and optoelectronic devices. Novel inorganic complexes are theoretically designed and investigated by doping superalkalis on Zn12O12 cluster. The results reveal that doping causes shifting of excess electrons from superalkalis towards Zn12O12 cluster and enhances the NLO properties of these isomers. Moreover, the effect of doping different superalkalis (Li3O, Na3O and K3O) over Zn12O12 nanocages is also studied. All the isomers have shown excellent NLO response and are transparent under ultraviolet region of workable laser conditions. Comparative analysis reveals that hyperpolarizability shows monotonic dependence on atomic number of metal atom in the superalkalis. K3O@Zn12O12 exhibits the highest first hyperpolarizability (βo) value of 394,217 au. The band gap is reduced up to 70% as compared to pristine nanocage, making them n-type semiconductors. This study provides a pathway for designing thermally stable inorganic complexes as potential precursors for high-performance NLO materials.
57 citations
TL;DR: First order hyperpolarizability of piroxicam is higher than that of isoxicam and tenoxicam, and Prediction of Activity Spectra gives activities, anti-inflammatory, CYP2C9 substrate and gout treatment.
47 citations
TL;DR: Theoretical calculations were done using density functional theory in order to determine vibrational frequencies, infrared and Raman intensities, MEP, NLO and NBO properties of the Hydrochlorothiazide-isoniazid (HCTA-IN) and HCTa-MA cocrystals.
TL;DR: In this article, a new organic compound of (Z) -N'- (2, 4-dinitrobenzylidene) -2- (quinolin-8-yloxy) acetohydrazide (DBQA) was synthesized for the first time and its structural characterization was performed by single crystal X-ray diffraction method.
TL;DR: In this article, pyrazinamide with p-toluenesulfonic acid and ferulic acid (PZFER) were investigated by density functional calculations to find geometrical parameters, wavenumbers and different molecular properties.
TL;DR: In this paper, the theoretical and experimental investigations of nonlinear optical properties of two chalcone derivatives were carried out by Z-scan technique using Q-switched Nd: YAG laser with 5'ns pulses at 532'nm.
Abstract: The present study reports the theoretical and experimental investigations of nonlinear optical properties of two novel chalcone derivatives namely (2E)-1-(Anthracen-9-yl)-3-(4-methoxyphenyl) prop-2-en-1-one (methoxy-ANC) and (2E)-1-(Anthracen-9-yl)-3-(4-ethoxyphenyl)prop-2-en-1-one (ethoxy-ANC). The theoretical calculations performed by density functional theory have been supported by the obtained experimental results. The FT-IR, FT-Raman and UV–visible absorption spectra were recorded and analysed. The optimized geometry, vibrational wavenumbers, HOMO-LUMO energy gap, Natural Bond Orbital (NBO) analysis, Natural Population Analysis (NPA) were computed by B3LYP level of theory with 6-311++G (d,p) basis set. The theoretical second-order hyperpolarizability were calculated using B3LYP and CAM-B3LYP hybrid functional. The third-order nonlinear optical properties, along with the optical limiting behaviour and laser damage threshold studies were carried out by Z-scan technique using Q-switched Nd: YAG laser with 5 ns pulses at 532 nm.
TL;DR: Li et al. as discussed by the authors designed a functionalized graphdiyne (GDY) material by adsorbing the tetrahedral Li3NM molecules on the largely delocalized π-conjugated GDY surface, and its structure, chemical stability, electronic property, and the first hyperpolarizability were investigated by using the density functional theory computations.
TL;DR: The obtained results suggest that compound 3 could have potential application as NLO material and provides valuable insight experimentally and theoretically, for designing new chemical entities to meet the demands of specific applications.
Abstract: The crystal and molecular structure of 5-(4-chlorophenyl)-2-amino-1,3,4-thiadiazole 3 was reported, which was characterized by various spectroscopic techniques (FT-IR, NMR and HRMS) and single-crystal X-ray diffraction. The crystal structure 3 (C8H6ClN3S) crystallized in the orthorhombic space group Pna21 and the unit cell consisted of 8 asymmetric molecules. The unit cell parameters were a = 11.2027(2) A, b = 7.6705(2) A, c = 21.2166(6) A, α = β = γ = 90°, V = 1823.15(8) A3, Z = 8. In addition, the structural geometry (bond lengths, bond angles, and torsion angles), the electronic properties of mono and dimeric forms of compound 3 were calculated by using the density functional theory (DFT) method at B3LYP level 6-31+ G(d,p), 6-31++ G(d,p) and 6-311+ G(d,p) basis sets in ground state. A good correlation was found (R2 = 0.998) between the observed and theoretical vibrational frequencies. Frontier molecular orbitals (HOMO and LUMO) and Molecular Electrostatic Potential map of the compound was produced by using the optimized structures. The NBO analysis was suggested that the molecular system contains N-H…N hydrogen bonding, strong conjugative interactions and the molecule become more polarized owing to the movement of π-electron cloud from donor to acceptor. The calculated structural and geometrical results were in good rational agreement with the experimental X-ray crystal structure data of 1,3,4-thiadiazol-2-amine, 3. The compound 3 exhibited n→π* UV absorption peak of UV cutoff edge, and great magnitude of the first-order hyperpolarizability was observed. The obtained results suggest that compound 3 could have potential application as NLO material. Therefore, this study provides valuable insight experimentally and theoretically, for designing new chemical entities to meet the demands of specific applications.
TL;DR: In this paper, a sequential study of rigidification of donating unit on its charge transfer towards accepting a coumarin unit, four donor-acceptor triphenylamine and N-phenyl carbazole based dyes were synthesized and characterized.
Abstract: In a sequential study of rigidification of donating unit on its charge transfer towards accepting a coumarin unit, four donor-acceptor triphenylamine and N-phenyl carbazole based coumarin dyes were synthesized and characterized. The dyes exhibit positive solvatochromism which is well supported by linear as well as multilinear regression analysis. The intramolecular charge transfer characteristics were established using Generalized Mulliken-Hush (GMH), and frontier molecular orbital (FMO), Molecular electrostatic potential (MEP) plot analysis from optimized geometry. The detailed investigation of positive acidochromism is performed. The non-linear optical (NLO) properties of synthesized dyes were studied using solvatochromic and computational method. The linear polarizability, hyperpolarizability and second-order hyperpolarizability of the synthesized dyes were studied by time-dependent density functional theory computational method using three different functionals with the basis set 6–31 G (d).
TL;DR: In this paper, the density functional theory calculations and spectroscopic characterization (FTIR, FT-Raman, 1H NMR and ultraviolet-visible) of the pharmaceutically active compound Cholesteno [4,6-b,c]-2′,5′-dihydro-1′, 5′-benzothiazepine (CHBT) have been carried out.
TL;DR: Ultrathin films demonstrate the best solution-based third-order nonlinear optical properties, featuring a nonlinear transmittance value of 0.54 and second hyperpolarizability value of 1.37 × 10-28 esu.
TL;DR: In this article, a chalcone derivative 4-methylbenzene-1-sulfonate (4MPMS) was grown by solvent evaporation technique and the structural properties have been carried out by powder XRD and single crystal XRD data.
TL;DR: In this article, four nonlinear optical chromophores based on the thiolated-isophorone-derived bridge have been synthesized and systematically investigated, and both the donor and bridge sections of the chromophore were functionalized with different isolation groups including tert-butyltrimethylsilane, tertbutyl(methyl)diphenylsilane and benzene ring, respectively.
Abstract: Four nonlinear optical chromophores A–D based on the thiolated-isophorone-derived bridge have been synthesized and systematically investigated. In particular, both the donor and bridge sections of the chromophores were functionalized with different isolation groups including tert-butyltrimethylsilane, tert-butyl(methyl)diphenylsilane, benzene ring and 1,2,3,4,5-pentafluorobenzene ring, respectively. All these four chromophores showed high thermal stabilities with decomposition temperatures above 220 °C. Most importantly, the rigid steric hindrance groups can effectively reduce the intermolecular electrostatic interactions to transform their hyperpolarizabilities into large electro-optic (EO) coefficients (r33). Polymeric thin films doped with 30 wt% chromophores A–D have been poled to afford large r33 values of 96, 143, 115, and 109 pm V−1 at 1.31 μm, respectively. Electro-optic performance together with density functional theory (DFT) calculations suggests that the isolation groups show different effects on the hyperpolarizability and poling efficiency of chromophores. The normalized r33 value of chromophore B increased to 8.36 × 10−19 pm cc per (V molecules) indicating the largest steric hindrance group and the highest polarization efficiency. All these results provide valuable insight into the understanding of the impact of isolation groups on macroscopic EO activities of materials.
TL;DR: In this paper, the authors synthesize l -pyroglutamic acid (abbreviated as LPGA) via intramolecular condensation of l -glutamic acids.
TL;DR: In this paper, a compound of 5-(2-Methoxy-4-(prop-1-en-1yl)phenoxy)pyrazine-2,3-dicarbonitrile was synthesized and structure was characterized by using XRD, FT-IR and NMR techniques.
TL;DR: This investigation provides a theoretical framework for conversion of centrosymmetric molecules into non-centrosy mmetric architectures to discover NLO candidates for modern hi-tech applications.
Abstract: Herein, we report the quantum chemical results based on density functional theory for the polarizability (α) and first hyperpolarizability (β) values of diacetylene-functionalized organic molecules (DFOM) containing an electron acceptor (A) unit in the form of nitro group and electron donor (D) unit in the form of amino group. Six DFOM 1–6 have been designed by structural tailoring of the synthesized chromophore 4,4′-(buta-1,3-diyne-1,4-diyl) dianiline (R) and the influence of the D and A moieties on α and β was explored. Ground state geometries, HOMO-LUMO energies, and natural bond orbital (NBO) analysis of all DFOM (R and 1–6) were explored through B3LYP level of DFT and 6-31G(d,p) basis set. The polarizability (α), first hyperpolarizability (β) values were computed using B3LYP (gas phase), CAM-B3LYP (gas phase), CAM-B3LYP (solvent DMSO) methods and 6-31G(d,p) basis set combination. UV-Visible analysis was performed at CAM-B3LYP/6-31G(d,p) level of theory. Results illustrated that much reduced energy gap in the range of 2.212–2.809 eV was observed in designed DFOM 1–6 as compared to parent molecule R (4.405 eV). Designed DFOM (except for 2 and 4) were found red shifted compared to parent molecule R. An absorption at longer wavelength was observed for 6 with 371.46 nm. NBO analysis confirmed the involvement of extended conjugation and as well as charge transfer character towards the promising NLO response and red shift of molecules under study. Overall, compound 6 displayed large and βtot, computed to be 333.40 (a.u.) (B3LYP gas), 302.38 (a.u.) (CAM-B3LYP gas), 380.46 (a.u.) (CAM-B3LYP solvent) and 24708.79 (a.u.), 11841.93 (a.u.), 25053.32 (a.u.) measured from B3LYP (gas), CAM-B3LYP (gas) and CAM-B3LYP (DMSO) methods respectively. This investigation provides a theoretical framework for conversion of centrosymmetric molecules into non-centrosymmetric architectures to discover NLO candidates for modern hi-tech applications.
TL;DR: The results revealed that alkali-metal fluorides favorably adsorb on the carbon surface, forming intramolecular electron donor-acceptor (D-π-A) pairs, and these complexes are rather stable against dissociation into fluorides, especially Li3F@GDY0/+ complexes.
Abstract: Graphene (GE), graphyne (GY) and graphdiyne (GDY) have promising applications because of their unique structural features with largely delocalized π-conjugated frameworks. Based on the density functional theory calculations, we investigated the adsorption behavior of alkali-metal fluorides (M3F, M = Li, Na, and K) on graphene, graphyne and graphdiyne, including the adsorption configurations, charge transfer, binding energy, and electrical conductivity. The electronic properties including orbital interactions and density of states (DOS) were also discussed. The results revealed that alkali-metal fluorides favorably adsorb on the carbon surface, forming intramolecular electron donor-acceptor (D-π-A) pairs, and these complexes are rather stable against dissociation into fluorides, especially Li3F@GDY0/+ complexes. Moreover, the adsorption of the fluorides largely affects the electronic structures of the 2D carbon materials. More importantly, it is found that the static first hyperpolarizability (βtot) of these complexes not only depends on the M3F fluorides but also on their charge-states, and these cationic M3F@GDY+ complexes exhibit large βtot values in order to establish their strong nonlinear optical (NLO) response, e.g., as high as ∼1.63 × 105 a.u. for Li3F@GDY+. However, the K3F@GE complex possesses the largest βtot value (4.59 × 105 a.u.), which is even preferable to the cationic M3F@GDY+ (M = Li, Na, and K) complexes, and the largest βtot value can be further explained by the crucial electronic transitions from TDDFT calculations. This study not only provides an effective strategy to design new carbon-based NLO optoelectronic materials, but it will also inevitably stimulate future experimental investigation for synthesis.
TL;DR: In this article, the electronic and nonlinear optical properties of transition metal (Sc, Fe, Cu, and Zn) substitutional doped C20 fullerenes are studied through DFT calculations.
Abstract: Electronic and nonlinear optical properties of transition metal (Sc, Fe, Cu, and Zn) substitutional doped C20 fullerenes are studied through DFT calculations. Replacement of carbon of C20 fullerene with a transition metal atom remarkably increases the hyperpolarizability (βo) of the system, compared to 0 au hyperpolarizability of pure C20 fullerene. The maximum βo is calculated for Sc–C19 (2224.5 au) followed by Fe–C19 (790.1 au), Cu–C19 (592.1 au), and Zn–C19 (564.6 au). The same order is found for the polarizability of the resulting systems. The polarizability and hyperpolarizabilities are found to decrease with increase in ionization potential of the doped transition metal. Molecular reactivity descriptors reveal that the iron-doped fullerene Fe–C19 is the softest system with the highest electrophilicity among all studied. The outcome of this study will be useful for promoting the possible use of the metal–fullerene systems as a new type of electronic nano-devices having good-performance nonlinear optical (NLO) properties.
TL;DR: In this article, a new organic compound 4-nitrophenol 4-aminobenzoic acid monohydrate (4NPABA) was synthesized and crystals were grown by slow evaporation solution technique (SEST).
TL;DR: The homologues of palkyl-p'-cynobhenyl (nCB) liquid crystal series are widely known for their diverse applications in display device industries, due to the low transition temperature as mentioned in this paper.
Abstract: The homologues of p-alkyl-p’-cynobiphenyl (nCB) liquid crystal series are widely known for their diverse applications in display device industries, due to the low transition temperature. Th...
TL;DR: In this paper, a series of novel D-π-A structure coumarin-benzoxazole derivatives have been synthesized, and the third-order NLO properties of the derivatives in DMSO are investigated by Z-scan measurement.
TL;DR: In this article, the authors investigated the efficiency on typical D-π-A molecular hyperpolarizabilities of 4-nitroaniline with a couple of point electric charge, together with configuration distortion and uniform external electronic field.