Assessment of the global and range-separated hybrids for computing the dynamic second-order hyperpolarizability of solution-phase organic molecules

• Published in: Theoretical chemistry accounts Vol. 133; no. 2
• Main Author: Lu, Shih-I
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.02.2014
• Subjects: Atomic/Molecular Structure and Spectra; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Organic Chemistry; Physical Chemistry; Regular Article; Theoretical and Computational Chemistry; Density functional theory; Global hybrids; Second-order hyperpolarizability; Range-separated hybrids
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-013-1439-4

The dynamic second-order hyperpolarizability from the third-harmonic generation experiment, 〈 γ 〉(−3 ω ; ω ; ω ; ω ), of 59 solution-phase organic molecules has been theoretically calculated and compared with available experimental data. The DFT/6-311+G(2d,p)//(CAM-)B3LYP/6-31G(2df,p) level of theory with the polarizable continuum model was employed to evaluate the static second-order hyperpolarizability. The theoretical static values were then corrected to dynamic estimates of 〈 γ 〉(−3 ω ; ω ; ω ; ω ) by employing a two-level approximation (Chen et al. in J Chem Phys 101(7):5860–5864, 1994 ). Calculated results showed that for the property of interest, the range-separated hybrids provided more accurate and consistent estimate than the global hybrids and the CAM-B3LYP optimized geometry delivered more accurate estimate than the B3LYP optimized geometry.