Application of discrete solvent reaction field to second-order susceptibility of organic molecular crystal

作者：Lu, Shih-I^*

来源：Theoretical Chemistry Accounts, 2016, 135(7): 180.

DOI：10.1007/s00214-016-1938-1

• Discrete solvent reaction field
• Organic molecular crystal
• Nonlinear optical property
• Density functional theory

This article presents an assessment of methods to study the second harmonic generation (SHG) response of organic molecular crystal. We incorporated the discrete solvent reaction field model, density functional theory, and the local field approximation (designated as the LF-DRF/DFT) to investigate the SHG susceptibilities of the chromophore of 2-carboxylic acid-4-nitropyridine-1-oxide (POA). In experiment, the POA appears in two different polymorphic crystal structures easily identified by noticeable differences in the melting points and SHG susceptibilities. In this work, we tried to utilize the LF-DRF/DFT in a supermolecular framework to differentiate the two crystals. While focusing on the ratio of the calculated SHG susceptibilities for the two crystals, at optical wavelength of 1064 nm, the S12 g and SSB-D exchange-correlation functionals within a 5 x 5 x 5 extended architecture produced 2.16 and 2.08, differing from the experimental estimate of 2.16 by 0 and 3.7 %, respectively.

• 出版日期2016-7-6
• 单位苏州大学