The first hyperpolarizability of p-nitroaniline in 1,4-dioxane: a quantum mechanical/molecular mechanics study.

In this work we have investigated the first hyperpolarizability of pNA in 1,4-dioxane solution using a quantum mechanics/molecular mechanics (QM/MM) model. The particular model adopted is the recently developed discrete solvent reaction field (DRF) model. The DRF model is a polarizable QM/MM model in which the QM part is treated using time-dependent density-functional theory and local-field effects are incorporated. This allows for direct computation of molecular effective properties which can be compared with experimental results. The solvation shift for the first hyperpolarizability is calculated to be 30% which is in good agreement with the experimental results. However, the calculated values, both in the gas phase and in solution, are by a factor of 2 larger than the experimental ones. This is in contrast to the calculation of the first hyperpolarizability for several small molecules in the gas phase where fair agreement is found with experimental. The inclusion of local-field effects in the calculations was found to be crucial and neglecting them led to results which are significantly larger. To test the DRF model the refractive index of liquid 1,4-dioxane was also calculated and found to be in good agreement with experiment.