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

Abstract

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 ), 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-charge embedding approach led to an attenuation of the second hyperpolarizability γ for all frequencies considered. Excitations of γ were not observed for frequencies smaller than 0.1 a.u. For the second hyperpolarizability (both static and dynamic), computational results showed that L-arginine phosphate monohydrate exhibits a large nonlinear optical effect, which implies the occurrence of microscopic third-order NLO behavior.

Chalcone as Potential Nonlinear Optical Material: A Combined Theoretical, Structural, and Spectroscopic Study

“…Here we consider a single BRC molecule and through the CHELPG scheme the crystalline environment polarization is simulated by considering the atoms that surrounding the BRC molecule as point charges. The SM approach was used in several theoretical works ,,− ,− and the obtained results were found close to the experimental ones. Particularly in ref , the DFT/CAM-B3LYP/6-311++G­(d,p) results for the nonlinear third-order susceptibility for a chalcone derivative have described satisfactorily the Z -scan experimental result of Prahbu et al…”

Effects of Changing Substituents on the Non-Linear Optical Properties of Two Coumarin Derivatives

“…The applicability of the SM approach is supported by its results close to the experimental ones [19][20][21]. Several recently published works use this technique due to the rapid convergence of NLO properties [22][23][24][25][26][27]. In the SM method, the atoms that form the surrounding molecules of the compounds are treated as point charges, since the interactions between molecules have a dominant electrostatic nature, taking into account long-range electrostatic effects [28,29].…”

Using the Supermolecule Approach To Predict the Nonlinear Optics Potential of a Novel Asymmetric Azine

“…The polarization of the crystalline environment was simulated by the supermolecule (SM) approach where the atoms of the molecules within the asymmetric unit are considered as point charges. This approach has been used in several works. − ,− In ref , the authors showed that SM approach simulates the dipole moment with results close to the experimental values and in refs and , the authors simulate the macroscopic properties χ (1) and χ (2) of the crystal, with results close to those of experiments. Other techniques to calculate the macroscopic properties χ (1) and χ (2) can also be cited, e.g., the works by Seidler and Champagne. , However, although the SM has provided good results, it is worth mentioning that other factors can also affect the nonlinear properties of the crystal.…”