Growth and characterization of nonlinear optical material, LAHClBr—a new member of L-arginine halide family

doi:10.1016/S0022-0248(01)01818-8

Journal of Crystal Growth

Volume 235, Issues 1–4, February 2002, Pages 523-528

https://doi.org/10.1016/S0022-0248(01)01818-8 Get rights and content

Abstract

Mixed crystals of two nonlinear optical materials, L-arginine hydrochloride monohydrate (LAHCl) and L-arginine hydrobromide monohydrate (LAHBr) have been grown from aqueous solution by slow evaporation at constant temperature (28°C) and also by slow-cooling method (0.5°C/day). The mixed crystal belongs to the monoclinic system with space group P2₁ and lattice parameters a=11.158(2) Å, b=8.579(3) Å, c=11.235(3) Å, β=91.55°(4). The mixed crystal is transparent down to 240 nm and its second harmonic generation efficiency for 1064 nm laser radiation is almost the same as that of parent crystals LAHCl and LAHBr. Whereas the damage threshold of the mixed crystal is higher than that of LAHBr but nearer to LAHCl.

Introduction

Within the last few years much progress has been made in the development of nonlinear optical (NLO) organic materials for second harmonic generation (SHG). However, most of the organic NLO crystals are constituted by weak van der Waals and hydrogen bonds. So they are soft in nature and it is difficult to cut and polish the crystal due to its softness. In view of this, a new type of NLO materials have been built from organic–inorganic complexes which form stronger ionic bond than the van der Waals and hydrogen bonds, thus increasing the mechanical strength of these semiorganic crystals. L-arginine phosphate monohydrate (LAP) discovered by Xu et al. [1] is one such semiorganic nonlinear optical material which has high nonlinear optical coefficients, high damage threshold, high angular sensitivity compared with potassium dihydrogen phosphate (KDP), the most widely used materials for SHG. Later on other salts of L-arginine have been synthesized [2], [3], [4], [5], [6], [7], [8], L-arginine hydrochloride monohydrate (LAHCl) and L-arginine hydrobromide monohydrate (LAHBr) are two such salts which can be grown easily and in appreciable sizes [7], [8]. A lot of work on these two crystals has been done in our laboratory [7], [8], [9], [10], [11], [12], [13], [14]. As a continuation of our research project on these L-arginine halide system we intended to grow mixed crystals of LAHCl and LAHBr. A mixed crystal is generally obtained by mixing two isomorphic crystals. Other than isomorphism, the lattice constants of the component crystals should be comparable. So LAHCl and LAHBr which satisfy all the above conditions are two ideal components to form a mixed system. Our intention to do this work was to improve the morphology of the crystals and to see how the optical and other physical properties of the parent crystals get changed due to this mixing. In these communication detail studies on synthesis, crystal growth, X-ray diffraction, DTA, TGA, SHG, transparency range, damage threshold measurement are presented.

Section snippets

Synthesis of LAHCl and LAHBr

LAHCl and LAHBr are synthesized in our laboratory according to the procedure described earlier [7], [8]. The materials were then purified by repeated crystallization in water.

Crystal growth

Equimolar solution of both LAHCl and LAHBr are mixed in a ratio of 1:1 of their volumes and the resultant mixture is allowed to evaporate at constant temperature (28°C) in a crystallizing vessel with perforated covers. This resulted into a large number of small crystals having rectangular bipyramidal shape (Fig. 1a).

Discussion

Mixed crystal of LAHCL and LAHBr (abbreviated as LAHClBr) which is obtained by reacting equimolar ratio of LAHCl and LAHBr forms a complex which is also crystallized in the same space group as the parent crystals. Comparison of the X-ray diffraction lines of LAHCl, LAHBr, LAHClBr (Fig. 2) shows that LAHCl and LAHBr are not disturbed in the crystallization process and retain their identity. Thermal analysis data of LAHClBr crystal show the presence of a sharp endothermic peak at 208°C

Conclusion

A new nonlinear optical crystal LAHClBr is grown from equimolar solution of LAHCl and LAHBr by slow evaporation as well as by slow-cooling method which crystallizes in the monoclinic space group with a=11.158(2) Å, b=8.579(3) Å, c=11.235(3) Å, β=91.55°(4). Different characterization method revealed that the mixed crystal is comparatively better than the parent crystals as far as the optical damage threshold and hardness are concerned. The mixing of equimolar LAHCl and LAHBr has little effect in

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DFT computations supported by B3LYP/cc-pVTZ level theory have been employed to derive equilibrium geometry, vibrational wavenumbers and the hyperpolarizability values of the nonlinear optical (NLO) material L-Arginine Hydrobromide monohydrate (LAHBr). Changes in the atomic charge distribution among different groups due to the presence of strong electronegative atoms and the attenuation of O-H bonds of water molecule have been analyzed. H-bonding effects of LAHBr are examined with the aid of structural analysis, IR, Raman vibrations and NBO analysis. The occurrence of strong intra- and intermolecular NH⋯O, NH⋯Br and OH⋯O ionic hydrogen bonding and non-bonded interactions in making the LAHBr unit NLO active has been discussed. The charge transport mechanism is analyzed by using dielectric measurements and the obtained results suggest good quality of the crystal.

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Growth and characterization of nonlinear optical material, LAHClBr—a new member of L-arginine halide family

Abstract

Introduction

Section snippets

Synthesis of LAHCl and LAHBr

Crystal growth

Discussion

Conclusion

J. Crystal Growth

J. Crystal Growth

J. Crystal Growth

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J. Crystal Growth