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

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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 (\( \overline{\alpha} \)) 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-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.

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Acknowledgements

The authors thank the following Brazilian agencies for financial support: Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento Pessoal de Nível Superior (CAPES), Fundação de Empreendimentos Científicos (FINATEC), Fundação de Amparo à Pesquisa do Distrito Federal (FAPDF), and Fundação de Amparo à Pesquisa do Estado de Goiás (FAPEG).

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Authors and Affiliations

  1. Campus Henrique Santillo, Universidade Estadual de Goiás, 75.132-903, Anápolis, GO, Brazil

    Clodoaldo Valverde & Rosemberg F. N. Rodrigues

  2. Universidade Paulista (UNIP), 74845-090, Goiânia, GO, Brazil

    Clodoaldo Valverde

  3. Laboratório de Estrutura Eletrônica e Dinâmica Molecular (LEEDMOL), Universidade de Brasília, Campus Darcy Ribeiro, Brasília, DF, Brazil

    Daniel F. S. Machado & Heibbe C. B. de Oliveira

  4. Instituto de Física, Universidade Federal de Goiás, 74001-970, Goiânia, GO, Brazil

    Basílio Baseia

  5. Departamento de Física, Universidade Federal da Paraíba, 58.051-970, João Pessoa, PB, Brazil

    Basílio Baseia

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  1. Clodoaldo Valverde
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  2. Rosemberg F. N. Rodrigues
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  3. Daniel F. S. Machado
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  4. Basílio Baseia
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  5. Heibbe C. B. de Oliveira
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Correspondence to Clodoaldo Valverde or Heibbe C. B. de Oliveira.

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This paper belongs to Topical Collection VI Symposium on Electronic Structure and Molecular Dynamics—VI SeedMol

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Valverde, C., Rodrigues, R.F.N., Machado, D.F.S. et al. Effect of the crystalline environment on the third-order nonlinear optical properties of L-arginine phosphate monohydrate: a theoretical study. J Mol Model 23, 122 (2017). https://doi.org/10.1007/s00894-017-3274-3

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