Ab initio calculations of multipole moments,polarizabilities and long-range interaction coefficients for the azabenzene molecules |
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Authors: | Fred Mulder Gerard van Dijk C Huiszoon |
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Institution: | 1. Institute of Theoretical Chemistry, University of Nijmegen, Toernooiveld , Nijmegen, The Netherlands;2. Chemical Physics Laboratory , Twente University of Technology , P.O. Box 217, Enschede, The Netherlands |
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Abstract: | Using LCAO-SCF wave functions on the monomers and a non-empirical Unsöld procedure for the second-order properties we have calculated the (2 l ) multipole moments (up to l=6), the (l,l') multipole polarizabilities (up to l + l' = 6) and the related long-range coefficients describing the electrostatic, induction and dispersion interactions for the different azabenzene molecules. The agreement with available experimental data is good, in particular for the dipole polarizabilities. The anisotropy of the long-range interaction potential is dominated by the electrostatic contributions, although the dispersion terms, especially the mixed-pole terms (l≠l') for even n (C8, C10), also contribute significantly; the induction energy is rather small. The π contributions to the polarizabilities and the dispersion interactions are found to be larger than earlier estimates. Moreover, it is shown by calculating the dipole polarizabilities of some (aza)naphthalenes and (aza)anthracenes, that a bond polarizability model can be applied effectively only if the delocalized π electrons are considered separately from the σ electrons. |
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