Rydberg character of the higher excited states of free-base porphin |
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| Authors: | Shigeyoshi Yamamoto Hiroshi Tatewaki Osamu Kitao Geerd H.F. Diercksen |
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| Affiliation: | (1) Faculty of Liberal Arts, Chukyo University, 101–2 Yagoto-Honmachi, Showa-ku, Nagoya 466-8666, Japan, JP;(2) Institute of Natural Sciences, Nagoya City University, Aichi 467-8501, Japan, JP;(3) National Institute of Materials and Chemical Research, Tsukuba, Ibaraki 305-8565 Japan, Graduate School of Engineering, the University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113–8565, Japan, JP;(4) Max-Planck-Institut für Astrophysik, Karl-Schwarzschild-Strasse 1, 85740 Garching, Germany, DE |
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| Abstract: | The Rydberg character of the excited states of free-base porphin (FBP) has been investigated by the ab initio configuration interaction singles (CIS) method and the state-averaged complete-active-space self-consistent-field method. Double-zeta basis sets augmented with s, p, and d Rydberg functions and d polarization functions have been employed. Two types of molecular orbitals sets, the restricted Hartree–Fock molecular orbitals obtained for the ground state (1A g ) and for the cation state (2A u ), have been used in the CIS calculations. All the calculations show that Rydberg-type excitations play important roles especially in the N bands. In this article we propose applying the model of a perturbed Rydberg series to interpret the excited states of FBP. By using this model, we have succeeded in analyzing the characteristics of the excited states as well as the experimental oscillator strengths, which have considerable magnitude even in the higher excited states. Received: 27 November 2000 / Accepted: 11 April 2001 / Published online: 27 June 2001 |
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| Keywords: | : Free-base porphin – Rydberg character – Perturber – Excited state – Configuration interaction |
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