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DFT/MRCI calculations on the excited states of porphyrin, hydroporphyrins, tetrazaporphyrins and metalloporphyrins

NASA Ames Research Center, MS 239-4, Moffett Field, CA 94035, USA

Corresponding author, Institute of Theoretical Chemistry and Structural Biology, University of Vienna, Althanstr. 14, 1090 Wien, Austria.

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and

STEFAN GRIMME

Organisch-Chemisches Institut der Universität Münster, Corrensstr. 40, 48149 Münster, Germany

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https://doi.org/10.1002/jpp.310Cited by:99 (Source: Crossref)

Abstract

A combination of density functional theory and multi-reference configuration interaction methods (DFT/MRCI) has been applied to the calculation of electronic absorption spectra in a series of porphyrin-type molecules. The calculated excitation energies and oscillator strengths for free-base porphyrin (PH₂) are in excellent agreement with experiment for both lower and higher excited states which are characterized by a significant contribution of double excitations (>20%). The 4¹B_2u, 4¹B_3u, and 5¹B_2u states are assigned to the L-band and the 7¹B_3u state to the M-band. The results for the hydroporphyrins chlorin (CH₂) and bacteriochlorin (BH₂) are in agreement with the experimentally observed increase in intensity for the Q-bands relative to PH₂. For BH₂ we predict a red shift of the Q_x-band (0.2 eV) and a blue shift of the B-band (0.5–0.7 eV) in comparison to both PH₂ and CH₂. For porphyrazine (PzH₂) and the commercial pigment phthalocyanine (PcH₂) the calculated oscillator strengths of the Q- and B-bands are of comparable size explaining the intense color of PcH₂. For the metalloporphyrins with magnesium (PMg) and zinc (PZn), the x- and y-polarized components of the Q- and B-bands collapse, due to the higher D_4h symmetry of the molecules. The calculations reproduce the slight, experimentally observed increase in the oscillator strength of the Q-band and the decrease for the B-band. These effects are ascribed to the electropositive nature of the metals relative to hydrogen. Except for the Q-bands, which are adequately described by the 'four-orbital model,' it is essential to account for excitations outside the four frontier orbitals as well as double and triple excitations for accurate reproduction of experimental data. We compare our results both with experiment and, where available, recent first-principle SAC-CI, MRMP, and TDDFT calculations.

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References

K. M. Kadish , K. M. Smith and R. Guilard (eds.) , The Porphyrin Handbook ( Academic Press , New York , 2000 ) . Google Scholar
A. Ghosh, The Porphyrin Handbook 7, eds. K. M. Kadish, K. M. Smith and R. Guilard (Academic Press, New York, 2000) p. 1. Google Scholar
I. Franket al., J. Chem. Phys. 108, 4060 (1998), DOI: 10.1063/1.475804. Crossref, Web of Science, Google Scholar
E. K. U. Gross, J. F. Dobson and M. Petersilka, Top. Curr. Chem. 181, 81 (1996), DOI: 10.1007/BFb0016643. Crossref, Web of Science, Google Scholar
R. Bauernschmitt and R. Ahlrichs, Chem. Phys. Lett. 256, 454 (1996), DOI: 10.1016/0009-2614(96)00440-X. Crossref, Web of Science, Google Scholar
R. E. Stratmann, G. E. Scuseria and M. J. Frisch, J. Chem. Phys. 109, 8218 (1998), DOI: 10.1063/1.477483. Crossref, Web of Science, Google Scholar
S. J. A. van Giesbergenet al., J. Chem. Phys. 111, 2499 (1999). Crossref, Web of Science, Google Scholar
D. Sundholm, Phys. Chem. Chem. Phys. 2, 2275 (2000), DOI: 10.1039/b001923m. Crossref, Web of Science, Google Scholar
D. Sundholm, Chem. Phys. Lett. 302, 480 (1999), DOI: 10.1016/S0009-2614(99)00194-3. Crossref, Web of Science, Google Scholar
S. Grimme, Chem. Phys. Lett. 259, 128 (1996), DOI: 10.1016/0009-2614(96)00722-1. Crossref, Web of Science, Google Scholar
A. B. J. Parusel and A. Ghosh, J. Phys. Chem. A 104, 2504 (2000), DOI: 10.1021/jp9921046. Crossref, Web of Science, Google Scholar
S. Grimme and M. Waletzke, J. Chem. Phys. 111, 5645 (1999), DOI: 10.1063/1.479866. Crossref, Web of Science, Google Scholar
T. Hashimotoet al., J. Phys. Chem. A 103, 1894 (1999), DOI: 10.1021/jp984807d. Crossref, Web of Science, Google Scholar
Y. Tokita, J. Hasegawa and H. Nakatsuji, J. Phys. Chem. A 102, 1843 (1998), DOI: 10.1021/jp9731361. Crossref, Web of Science, Google Scholar
J. Hasegawaet al., J. Phys. Chem. B 102, 1320 (1998), DOI: 10.1021/jp972894o. Crossref, Web of Science, Google Scholar
K. Toyota, J. Hasegawa and H. Nakatsuji, Chem. Phys. Lett. 250, 437 (1996), DOI: 10.1016/0009-2614(96)00043-7. Crossref, Web of Science, Google Scholar
K. Toyota, J. Hasegawa and H. Nakatsuji, J. Phys. Chem. A 101, 446 (1997), DOI: 10.1021/jp9617635. Crossref, Web of Science, Google Scholar
J. Hasegawaet al., Chem. Phys. Lett. 250, 159 (1996), DOI: 10.1016/0009-2614(95)01406-3. Crossref, Web of Science, Google Scholar
D. Sundhom, Chem. Phys. Lett. 317, 392 (2000). Crossref, Web of Science, Google Scholar
A. Ghosh, Acc. Chem. Res. 31, 189 (1998), DOI: 10.1021/ar950033x. Crossref, Web of Science, Google Scholar
R. Ahlrichset al., Chem. Phys. Lett. 162, 165 (1989), DOI: 10.1016/0009-2614(89)85118-8. Crossref, Web of Science, Google Scholar
O. Treutler and R. Ahlrichs, J. Chem. Phys. 102, 346 (1995), DOI: 10.1063/1.469408. Crossref, Web of Science, Google Scholar
T. H. Dunning and P. J. Hay , Modern Theoretical Chemistry 3 , ed. H. F. Schaefer III ( Plenum Press , New York , 1977 ) . Google Scholar
A. D. Becke, J. Chem. Phys. 98, 1372 (1993), DOI: 10.1063/1.464304. Crossref, Web of Science, Google Scholar
L. Edwardset al., J. Mol. Spectrosc. 38, 16 (1971), DOI: 10.1016/0022-2852(71)90090-7. Crossref, Web of Science, Google Scholar
S. R. Gwaltney and R. J. Bartlett, J. Chem. Phys. 108, 6790 (1998), DOI: 10.1063/1.476094. Crossref, Web of Science, Google Scholar
M. Nooijen and R. J. Bartlett, J. Chem. Phys. 106, 6449 (1997), DOI: 10.1063/1.473635. Crossref, Web of Science, Google Scholar
L. Serrano-Andréset al., Chem. Phys. Lett. 295, 195 (1998). Crossref, Web of Science, Google Scholar
O. Kitao, H. Ushiyama and N. Mirua, J. Chem. Phys. 110, 2936 (1999), DOI: 10.1063/1.477937. Crossref, Web of Science, Google Scholar
H. Nakatsuji, J. Hasegawa and M. Hada, J. Chem. Phys. 104, 2321 (1996), DOI: 10.1063/1.470927. Crossref, Web of Science, Google Scholar
C. K. Chang, Biochem. 19, 1971 (1980). Crossref, Web of Science, Google Scholar
H. Scheer and H. H. Inhoffen, The Porphyrins II, ed. D. Dolphin (Academic Press, New York, 1978) p. 45. Crossref, Google Scholar
M. Gouterman , The Porphyrins III , ed. D. Dolphin ( Academic Press , New York , 1978 ) . Crossref, Google Scholar
U. Nagashimaet al.T. Kashiwagiet al., J. Chem. Phys. 85, 4524 (1986), DOI: 10.1063/1.451773. Crossref, Web of Science, Google Scholar
C. Weiss , The Porphyrins III , ed. D. Dolphin ( Academic Press , New York , 1978 ) . Crossref, Google Scholar
R. P. Linstead and M. Whally, J. Chem. Soc. 4839 (1952), DOI: 10.1039/jr9520004839. Web of Science, Google Scholar
G. E. Ficken and R. P. Linstead, J. Chem. Soc. 4847 (1952). Web of Science, Google Scholar
E. Orti and J. L. Brédas, J. Chem. Phys. 89, 1009 (1988), DOI: 10.1063/1.455251. Crossref, Web of Science, Google Scholar
L. Edwards, D. H. Dolphin and M. Gouterman, J. Mol. Spectrosc. 35, 90 (1970), DOI: 10.1016/0022-2852(70)90168-2. Crossref, Web of Science, Google Scholar
G. D. Dorough, J. R. Miller and F. M. Huennekens, J. Am. Chem. Soc. 73, 4315 (1951), DOI: 10.1021/ja01153a085. Crossref, Web of Science, Google Scholar
Yalman R., Spaulding L. Porphin Project Final Report, 1968; Unpublished . Google Scholar