Uncoupled Hartree-Fock calculations of the polarizability and hyperpolarizabilities of nitrophenols

The polarizability and hyperpolarizabilities of nitrophenols as model compounds for studying nonlinear optics have been investigated at the Hartree-Fock level of approximation by means of the Dalgarno Uncoupled Hartree-Fock (DUHF) or Sum Over Orbitals (SOO) method. The additive character and the charge transfer effects in α,β,γ and have been analyzed in terms of the δ and π molecular orbital contributions, the contribution of the individual π molecular orbitals, and the contribution of the highest occupied and the lowest unoccupied\ud molecular orbitals. Within the SOO approach, the reliability of the Two-Level Model has been tested and the influence of the rotation of the nitro group and of the presence of the intramolecular hydrogen bonding in ortho-nitrophenol have been studied. The results show that the present method is a reliable and efficient tool for the prediction of trends in the molecular polarizability and hyperpolarizabilities of large molecule

Two ground state conformers of the proton sponge 1,8-bis(dimethylamino)naphthalene revealed by fluorescence spectroscopy and ab-initio calculations

The S1 S0 transitions of the "proton sponge" 1,8-bis(dimethylamino)naphthalene have been studied by experiment and ab initio calculations. Fluorescence excitation and single vibronic level emission spectroscopy on the sample seeded in a supersonic expansion lead to the conclusion that the molecule can adopt two conformations in the ground state. This conclusion is supported by ab initio calculations at the HF/6-31G* level. The most stable conformer is shown to carry the spectroscopic characteristics of the naphthalene chromophore, while torsional motions of the dimethylamino groups dominate the spectroscopy of the other conformer