Q. Valence and Rydberg states of organic aromatic compounds

 

A. For substituted benzenes such as aniline or p-benzoquinone, the basis sets we used were Huzinaga-Dunning’s (9s5p/4s)/[5s3p/3s] with standard scaling factors plus Huzinaga’s polarization functions([2d] for C, N and O, [1p] for H), Dunning’s diffuse anion basis ([1s1p] for C, [2s2p] for N, O) split with the standard splitting factors.  They were augmented with Dunning’s Rydberg functions (3s, 3p, and 3d functions of carbon split into [2s2p2d] with standard splitting factors) at the center of the molecule. (See J. Phys. Chem. A., 106, 3838-3849 (2002) for p-benzoquinone and J. Chem. Phys., 117, 2045-2052 (2002) for aniline.)

For five-membered ring compounds such as furan, pyrrole and thiophen, or azabenzene such as pyridine, we used Dunning’s augmented correlation consistent polarized triple zeta basis sets, AUG-cc-pVTZ, for O, N, S and C atoms with one f polarization function removed for all C atoms, and cc-pVTZ for H atoms. Additionally, a set of diffuse functions (5s5p5d) were placed on the molecular center of gravity to investigate the Rydberg states in a wide energy region. (See J. Chem. Phys., 113, 7853-7866 (2000) for furan and pyrolle, J. Chem. Phys., 114, 842-850 (2001) for thiophen, and J. Chem. Phys., 114, 5117-5123 (2001) for pyridine.)