Abstract
Quantum-chemical calculations of the electronic structure of the tetraphenylporphin dication have been made by the CNDO/S method for various values of the parameter of saddle-like distortions of the porphyrin macroring of angle ϕ and the dihedral angle Θ between the macroring planes and the phenyl rings. It is shown that the boundary highest occupied molecular orbital (HOMO) of symmetry a 2u is the most sensitive to variations in ϕ and Θ and its order can be changed relative to another HOMO of symmetry a 1u . The behavior of the lower excited electronic singlet and triplet states depending on ϕ and Θ has been analyzed in detail. In particular, the addition of configurations with charge transfer to the Q, B, and N states as well as to the T 1 and T 2 states has been determined quantitatively. An interpretation of the experimental spectra of porphyrin dications on the basis of the calculation results is given.
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REFERENCES
D. E. Tronrud, M. F. Schmid, and B. W. Matthews, J. Mol. Biology, 188, 443–454 (1986).
J. Deisenhofer and H. Michel, Angew. Chem., Int. Ed. Engl., 28, 829–847 (1989).
R. G. Alden, M. R. Ondrias, and J. A. Shelnutt, J. Am. Chem. Soc., 112, 691–697 (1990).
K. M. Barkigia, L. Chantranupong, K. M. Smith, and J. Fajer, J. Am. Chem. Soc., 110, 7566–7567 (1988).
S. Tsuchiya, Chem. Phys. Lett., 169, 608–610 (1990).
J. Takeda, T. Ohya, and M. Sato, Chem. Phys. Lett., 183, 384–386 (1991).
K. M. Barkigia, M. W. Renner, L. R. Furenlid, C. J. Medforth, K. M. Smith, and J. Fajer, J. Am. Chem. Soc., 115, 3627–3635 (1993).
S. Gentemann, C. J. Medforth, T. P. Forsyth, D. J. Nurco, K. M. Smith, J. Fajer, and D. Holten, J. Am. Chem. Soc., 116, 7363–7368 (1994).
M. Ravikanth and T. K. Chandrashekar, J. Photochem. Photobiol. A: Chem., 74, 181–187 (1993).
N. C. Maiti and M. Ravikanth, J. Chem. Soc., Faraday Trans., 92, 1095–1100 (1996).
S. Gentemann, C. J. Medforth, T. Ema, N. Y. Nelson, K. M. Smith, J. Fajer, and D. Holten, Chem. Phys. Lett., 245, 441–447 (1995).
P. Charlesworth, T. G. Truscott, D. Kessel, C. J. Medforth, and K. M. Smith, J. Chem. Soc. Faraday Trans., 90, 1073–1076 (1994).
S. Gentemann, S. H. Leung, K. M. Smith, J. Fajer, and D. Holten, J. Phys. Chem., 99, 4330–4334 (1995).
A. Regev, T. Galili, C. J. Medforth, K. M. Smith, K. M. Barkigia, J. Fajer, and H. Levanon, J. Phys. Chem., 98, 2520–2526 (1994).
V. V. Sapunov and G. D. Egorova, Khim. Fiz., 13, 60–67 (1994).
S. Gentemann, N. Y. Nelson, L. Jaquinod, D. J. Nurco, S. H. Leung, C. J. Medforth, K. M. Smith, J. Fajer, and D. Holten, J. Phys. Chem. B, 101, 1247–1254 (1997).
V. I. Gael', V. A. Kuz'mitskii, and K. N. Solov'ev, Zh. Prikl. Spektrosk., 63, 932–942 (1996).
V. N. Knyukshto, K. N. Solovyov (Solov'ev), and G. D. Egorova, Biospectroscopy, 4, 121–133 (1998).
V. N. Knyukshto, K. N. Solov'ev, A. F. Mironov, G. D. Egorova, and A. V. Efimov, Opt. Spektrosk., 85, 592–600 (1998).
A. Stone and E. V. Fleischer, J. Am. Chem. Soc., 90, 2735–2748 (1968).
B. Cheng, O. Q. Munro, H. M. Marques, and W. R. Scheidt, J. Am. Chem. Soc., 119, 10732–10742 (1997).
V. I. Gael', V. A. Kuz'mitskii, and K. N. Solov'ev, Zh. Prikl. Spektrosk., 66, 559–562 (1999).
B. M. L. Chen and A. Tulinsky, J. Am. Chem. Soc., 94, 4144–4151 (1972).
K. M. Barkigia, M. D. Berber, J. Fajer, C. J. Medforth, M. W. Renner, and K. M. Smith, J. Am. Chem. Soc., 112, 8851–8857 (1990).
V. A. Kuz'mitskii, Investigation of Excited Electronic States of Metalloporphyrin Dimers by the Method of Self-Congruent Field of Molecular Orbitals and Linear Combination of Atomic Orbitals, Preprint No. 188 of the Institute of Physics, Academy of Sciences of Belarus [in Russian], Minsk (1988).
A. V. Luzanov, Usp. Khim., 49, 2086–2117 (1980).
A. Stern and H. E. Wenderlein, Z. Phys. Chem., A175, 405–437 (1936).
N. E. Gruhn, D. L. Lichtenberger, H. Ogura, and F. A. Walker, Inorg. Chem., 38, 4023–4027 (1999).
J. D. Petke, G. M. Maggiora, L. L. Shipman, and R. E. Christoffersen, J. Mol. Spectrosc., 71, 64–84 (1978).
V. S. Chirvonyi, E. I. Sagun, and B. M. Dzhagarov, Zh. Prikl. Spektrosk., 27, 167–170 (1977).
V. L. Ermolaev and E. B. Sveshnikova, Acta Phys. Polonica, 30, 771–790 (1968).
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Gael', V.I., Kuz'mitskii, V.A. & Solov'ev, K.N. Influence of Nonplanar Distortions of the Tetrapyrrole Macroring on the Electronic States of the Tetraphenylporphin Dication. Journal of Applied Spectroscopy 67, 956–965 (2000). https://doi.org/10.1023/A:1004112102893
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DOI: https://doi.org/10.1023/A:1004112102893