Comparison of Static First Hyperpolarizabilities Calculated with Various Quantum Mechanical Methods

Abstract

The prediction of nonlinear electro-optic (EO) behavior of molecules with quantum methods is the first step in the development of organic-based electro-optic devices. Typical EO molecules may require calculations with several hundred electrons, which prevents all but the fastest methods (semiempirical and density functional theory (DFT)) from being used for EO estimation. To test the reliability of these methods, we compare dipole moments, polarizabilities, and first-order hyperpolarizabilities for a wide range of structures of experimental interest with Hartree-Fock (HF), intermediate neglect of differential overlap (INDO), and DFT methods. The relative merits of molecules are consistently predictable with every method.

A novel NIR violanthrone derivative with high electron-deficiency: effect of fluorescence on dicyanomethylene substitution

“…As is well known, cyano group is a kind of very strong electron-acceptor that is broadly applied in many intramolecular charge-transferring (ICT) systems [21][22][23]. Therefore, four cyano groups (two strong electron-withdrawing dicyanomethylene unit) were incorporated into carbonyl groups through Knoevenagel reaction (VA-CN, Figure 1).…”

Systematic comparison of DFT and CCSD dipole moments, polarizabilities and hyperpolarizabilities

“…Density functional theory calculations of polarizabilities and hyperpolarizabilities for small molecules have proven to be in good to reasonable agreement with results obtained from wave function based correlated methods and gas phase experiments [18][19][20][21][22]. However, for one dimensional conjugated systems such as polyacetylene and elongated push pull polyenes it has been shown in [23,24] and references therein that DFT overestimates polarizabilities and hyperpolarizabilities.…”

Using phenoxazine and phenothiazine as electron donors for second-order nonlinear optical chromophore: Enhanced electro-optic activity

“…The DFT calculations were carried out at the hybrid B3LYP level by employing the split valence 6e311 g (d, p) basis set [38,39] to understand the ground-state polarization of the chromophores with different donors. All molecules were assumed to be in transconfigurations.…”