L-Argininium phosphite - a new candidate for NLO materials (2025)

An efficient piezoelectric single-crystal l-argininium phosphite: structural, Hirshfeld, electrical and mechanical analyses for NLO applications

Applied Physics A, 2019

l-Argininium phosphite, nonlinear optical crystal was grown by the slow evaporation solution growth technique. It crystallizes in the monoclinic system, with P2 1 space group and dimensions of unit cells are a = 9.3677 Å, b = 4.8601 Å and c = 13.2096 Å. Its morphology was simulated and indexed using WinXMorph program. The contribution of different interactions in the crystal structure was discerned visually using Hirshfeld surface analysis. The positions of NMR signal (δ) corresponding to carbon and hydrogen atoms in titled molecule were recorded using HETCOR analysis. Moreover, the titled compound's crystallinity was examined by performing omega scan. Through UV-Vis-NIR transmittance spectra, the cutoff wavelength and bandgap for titled crystal were evaluated. Its dielectric constant and losses were investigated as frequencies varied at room temperature. Furthermore, laser and shock damage threshold analysis were employed on titled compound. Its piezoelectric charge coefficient was also determined and found to be 12 pC/N along (010) plane. Kurtz and Perry's technique was used to measure its second harmonic generation (SHG) efficiency, which was observed to be 20 mV taking standard KDP as reference.

Effect of the crystalline environment on the third-order nonlinear optical properties of L-arginine phosphate monohydrate: a theoretical study

Journal of molecular modeling, 2017

A supermolecular approach combined with an iterative electrostatic scheme was employed to investigate the nonlinear optical properties of the hybrid L-arginine phosphate monohydrate crystal, the procedure being aided by DFT calculations. The supermolecular scheme basically treated the molecules surrounding the unit cell as point charges; this approximation results in rapid convergence, making it a feasible method. DFT functionals of different flavors were considered: B3LYP, B2PLYP, CAM-B3LYP, ωB97, and M06HF, utilizing the 6-311 + G(d) basis set. All functionals gave sufficiently accurate values for the dipole moment (μ) with respect to the experimental value 32(2) D. For the average linear polarizability ([Formula: see text]) and the total first hyperpolarizability (β tot), good agreement was observed between the DFT-calculated values and MP2-derived results reported in the literature. For the second hyperpolarizability, both static and dynamic regimes were considered. The point-ch...

Electron density study of a new non-linear optical material: L-arginine phosphate monohydrate (LAP). Comparison between X–X and X–(X + N) refinements

Acta Crystallographica Section B Structural Science, 1996

The crystal structure, thermal vibrations and electron density of L-arginine phosphate monohydrate (formally C6H15N40~.H2PO4-.H20) have been analysed using 130 K single-crystal X-ray diffraction data to a resolution of (sin0/A)max = 1.20,&-1. A multipolar pseudoatom density model was fitted against the 6805 observed data with I > 3o-(/), [R(F) = 0.016,Rw(F) = 0.014, S = 1.39] in order to map the static valence-electron density distribution. Positional and thermal vibration parameters for H atoms were taken from neutron diffraction results. A comparison between the electron density p(r), ~72p(r) and the electrostatic potential calculated from X-X and X-(X + N) refinements shows that reliable results may be obtained from X-X data only.

Spectroscopic study of l-arginine interaction with potassium dihydrogen phosphate crystals

Journal of Materials Research, 2009

Inorganic potassium dihydrogen phosphate (KDP) is widely known for its value as a nonlinear optical material. In this study, pure and l-arginine–doped KDP single crystals were grown by the slow solvent evaporation technique and further subjected to infrared absorption and Raman studies for the confirmation of chemical group functionalization and possible bonding between the organic and inorganic materials. The appearance in the infrared absorption spectra of additional vibrational lines, which mostly originate from disturbed N–H, C–H, and C–N bonds of the l-arginine–doped salt, confirm the interaction between KDP and the organic material. This affirmation is supported by more evidence from Raman measurements, where the disappearance of NH vibrations of the amino group is observed. We are thus led to the possibility of hydrogen bonding primarily between the nucleophilic O− of the phosphate unit of KDP and the amino group of the l-arginine.

Synthesis, Growth, and Characterization of l-Arginine Acetate Crystal:  A Potential NLO Material

Crystal Growth & Design, 2003

Single crystals of nonlinear optical material L-arginine acetate (LAA) (C 6 H 14 N 4 O 2 ‚CH 3 COOH), space group P2 1 , were successfully grown for the first time by the temperature-lowering method and also by the slow evaporation method at constant temperature (30°C) from its aqueous solution with pH at 6 and dimension of 21 × 15 × 3 mm 3. Initially, solubility tests were carried out for four solvents such as water, water and methanol, water and ethanol, and water and acetone. Among the four solvents, the solubility of LAA was found to be the highest in water, so crystallization of LAA was done from its aqueous solution. Morphological analysis reveals that the crystal is a polyhedron with 16 developed faces with major face forms {100}, {001}, and {102} (pinacoids) parallel to the polar axis. As grown crystals were characterized by chemical analysis, density measurement, and X-ray powder diffraction studies. Infrared spectroscopy, thermogravimetric analysis, and differential thermal analysis measurements were performed to study the molecular vibration and thermal behavior of LAA crystals. Thermal analysis does not show any structural phase transition.

[NH4]12[(MoO2)2O(HPO4)2]4[PO4]Cl·0.5H2O: A mixed phosphomolybdate with nonlinear optical properties

Inorganica Chimica Acta, 2019

Phosphates usually have shorter ultraviolet (UV) absorption edges and are ideal for deep-UV nonlinear optical (NLO) applications. The introduction of d 0 transition metal cation Mo 6+ into phosphates can facilitate to increase the distortion of the crystal structure and therefore it is easy to obtain the noncentrosymmetric (NCS) compounds, which are expected for NLO materials. In the work, the crystals of an ammonium molybdenophosphate chloride [NH 4 ] 12 [(Mo 2) 2 O(HPO 4) 2 ] 4 [PO 4 ]Cl•0.5H 2 O (AMPC) were grown by hydrothermal method. The second harmonic generation (SHG) of the compound exhibits 0.3 × KH 2 PO 4 (KDP) at 1064 nm radiation and the cutoff edge of it is about 230 nm. The crystal structure is consist of unique [Mo 4 P 4 O 32 H 4 ] 16− units and further to form layer two-dimensional (2D) structure. The first-principles electronic structure calculations show that the NLO response of it mainly comes from the MoO units. We also studied UV-vis-NIR diffuse reflectance, infrared spectrum and thermal properties of the compound. Additional, by the investigation of similar phosphomolybdates, we found that they have high ratios of NCS crystal structures about 39%.

Linear and nonlinear optical properties, pyroelectricity and vibrational spectroscopy of polar guanidinium hydrogen phosphite, GuH2PO3, and hydrogen selenite, GuHSeO3

Optical Materials, 2021

For the non-centrosymmetric guanidinium compounds GuH 2 PO 3 and GuHSeO 3 with polar symmetry P2 1 a fundamental characterization as optical materials is given, including X-ray crystal structure analysis and a vibrational spectroscopy (Raman and IR) study. In addition, for both polar crystals the pyroelectric coefficients and their temperature dependence are evaluated. Using large single crystals grown from aqueous solution, refractive indices and their dispersion in the wavelength range 435-1083 nm are determined by the prism method. From the data phase matching conditions for collinear second harmonic generation (SHG) are analysed. Both crystals allow the realization of phase matching for SHG of both, type I and type II processes. Quantification of SHG properties was performed for both powdered salts and GuH 2 PO 3 single crystals. The measurements of the pyroelectric coefficients in the temperature range 100-340 K show pronounced pyroelectricity but no indication for ferroelectric behaviour of the two crystals.

Optical properties of L-arginine doped potassium dihydrogen phosphate crystals

Inorganic potassium dihydrogen phosphate (KDP) is widely known for its value as a nonlinear optical material. In this study, pure and L-arginine-doped KDP single crystals were grown by the slow solvent evaporation technique and further subjected to infrared absorption and Raman studies for the confirmation of chemical group functionalization and possible bonding between the organic and inorganic materials. The appearance in the infrared absorption spectra of additional vibrational lines, which mostly originate from disturbed N-H, C-H, and C-N bonds of the L-arginine-doped salt, confirm the interaction between KDP and the organic material. This affirmation is supported by more evidence from Raman measurements, where the disappearance of NH vibrations of the amino group is observed. We are thus led to the possibility of hydrogen bonding primarily between the nucleophilic O À of the phosphate unit of KDP and the amino group of the L-arginine.

Structural and Optical Properties of NLO Material: 4-Sulfamoylanilinium Dihydrogen Phosphate

FT-IR and FT-Raman spectra of 4-sulfamoylanilinium dihydrogen phosphate were recorded at room temperature and analyzed. The vibrational wavenumbers were also computed by using the HF and B3LYP methods invoking 6-311++G(d,p) basis set and compared with the experimental values. Also in this present work, the optimized molecular structure and calculated geometrical parameters of the title compound was compared with the previously published experimental (XRD) molecular structure and geometrical parameters. The Mulliken population analyzes were carried out for the optimized molecular geometry by HF and B3LYP methods. This study reiterate the intermolecular charge transfer occur between the ions. The electronic properties such as HOMO and LUMO energies were performed by HF and DFT/B3LYP level of theory. The narrow energy gap between HOMO and LUMO makes the molecule to be possibly biological/pharmaceutical active and the high chemical reactivity. The transparency of the crystal was analyzed by using the UV-Visible spectroscopy. The optical band of the title compound was found to as 5.57 eV. The large band gap and lower cut off wavelength at 223 nm confirms the suitability of the crystal for optical applications.

Synthesis, growth and characterization of l-alaninium oxalate - a novel organic NLO crystal

Crystal Research and Technology, 2007

Nonlinear optical material of L-alaninium oxalate (LAO) has been synthesized and single crystals are grown by slow evaporation technique. The solubility data of LAO is determined in water. Single crystal X-ray diffraction study showed that LAO belongs to orthorhombic system with a non-centrosymmetric space-group P2 1 2 1 2 1 . The functional groups have been identified from FT-IR spectrum. The UV-Vis-NIR spectrum of LAO shows less optical absorption in the entire visible region. The second harmonic generation (SHG) in the material was estimated using Nd:YAG laser. The mechanical properties of the grown crystals are studied using Vickers microhardness tester. The AC and DC conductivity, and dielectric studies are also carried out and reported for the first time.