Theoretical Evaluation of Hyperpolarizability of L-2-Pyrrolidone-5-carboxylic Acid (L-PCA)

L-2-Pyrrolidone-5-carboxylic acid (L-PCA) is a novel nonlinear optical material with the optical transparent range down to the UV region. L-PCA molecules are hydrogen-bonded to form the three-dimensional network in a crystal. It has been thought that the network of hydrogen bonds influences on the stability of the crystal structure as well as the second-order optical nonlinearity. We have performed the theoretical evaluation of the contributions of the intermolecular hydrogen bonds to structural stability and second-order nonlinearity in the L-PCA crystals by use of the molecular orbital calculation methods. In the calculation of CNDO/S-SECI (singly excited configuration interaction) method, it is shown that the primary contributor to the molecular hyperpolarizability (β) is an nπ → π* transition in the amide moiety of L-PCA molecule. The calculation of intermolecular interaction energies for L-PCA clusters by the ab initio STO-3G method indicates that the hydrogen bonds in the crystal contribute to the s...

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