Geometric structures and excited electronic states for free bases of bacteriochlorin (H2BC) and tetraazabacteriochlorin (H2TABC) as well as for their magnesium complexes (MgBC and MgTABC), analogs of bacteriopheophytin a (H2BPhea) and bacteriochlorophyll a (MgBPhea), have been calculated by a DFT method and by an INDO/Sm method (the INDO/S method with parameterization modified by the authors), respectively. The factors responsible for the observed bathochromic shift of the long-wavelength Q x (0–0) band of MgBPhea relative to H2BPhea, \( {{\updelta }}{E_{{Q_x}}} \cong - 300\;{\text{c}}{{\text{m}}^{ - 1}} \), have been clarified. Contributions of one- and two-electron interactions to the resulting shift of the Q x (0–0) band have been analyzed in detail for the H2BC/MgBC, H2TABC/MgTABC, and porphine (H2P)/Mg porphine (MgP) pairs. It is shown that the bathochromic shift under consideration for the tetrahydro derivatives is caused by a decrease of the orbital energy gap ε1–ε−1 between the lowest unoccupied and highest occupied molecular orbitals. The variation of δ(ε1–ε−1) is large and amounts to –1660 and –920 cm–1 for the H2BC/MgBC and H2TABC/MgTABC pairs, respectively. The two-electron contributions, both into the energy of electronic configurations and due to the superposition of the configurations, produce a compensating hypsochromic effect such that the shifts \( {{\updelta }}{E_{{Q_x}}} \) are –260 and –150 cm–1 for the H2BC/MgBC and H2TABC/MgTABC pairs, respectively. It is also shown that the calculated electronic spectra for the considered molecules agree quantitatively with the experimental absorption spectra.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. F. Mironov, M. A. Grin, A. G. Tsiprovskii, A. V. Segenevich, D. V. Dzardanov, K. V. Golovin, A. A. Tsygankov, and Ya. K. Shim, Bioorg. Khim., 29, 214–221 (2003).
G. P. Gurinovich, A. N. Sevchenko, and K. N. Solovyov, Spectroscopy of Chlorophyll and Related Compounds [in Russian], Nauka i Tekhnika, Minsk (1968), pp. 192–193.
K. M. Smith, ed., Porphyrins and Metalloporphyrins, Elsevier, Amsterdam–New York–Oxford (1975).
G. Hartwich, L. Fiedor, I. Simonin, E. Cmiel, W. Schafer, D. Noy, A. Scherz, and H. Scheer, J. Am. Chem. Soc., 120, 3675–3683 (1998).
T. Fukuda, E. A. Makarova, E. A. Luk’yanets, and N. Kobayashi, Chem. Eur. J., 10, 117–133 (2004).
P. P. Pershukevich, V. A. Galievskii, A. S. Stashevskii, E. A. Makarova, E. A. Luk’yanets, and K. N. Solovyov, Zh. Prikl. Spektrosk., 77, No. 6, 852–865 (2010).
V. A. Kuzmitsky and D. I. Volkovich, Zh. Prikl. Spektrosk., 75, No. 1, 28–35 (2008).
L. Petit, C. Adamo, and N. Russo, J. Phys. Chem. B, 109, 12,214–12,221 (2005).
L. Petit, A. Quartarolo, C. Adamo, and N. Russo, J. Phys. Chem. B, 110, 2398–2404 (2006).
I. Lanzo, N. Russo, and E. Sicilia, J. Phys. Chem. B, 112, 4123–4130 (2008).
D. N. Laikov, Chem. Phys. Lett., 281, 151–156 (1997).
L. L. Gladkov, V. V. Gromak, and V. K. Konstantinova, Zh. Prikl. Spektrosk., 74, No. 3, 296–299 (2007).
D. I. Volkovich, V. A. Kuzmitsky, and P. A. Stuzhin, Zh. Prikl. Spektrosk., 75, No. 5, 606–622 (2008).
V. N. Knyukshto, V. A. Kuzmitsky, E. A. Borisevich, D. I. Volkovich, A. S. Bubnova, P. A. Stuzhin, and K. N. Solovyov, Zh. Prikl. Spektrosk., 76, No. 3, 365–375 (2009).
K. N. Solovyov, P. A. Stuzhin, V. A. Kuzmitsky, D. I. Volkovich, V. N. Knyukshto, E. A. Borisevich, and A. Ul-Haque, Makrogeterotsikly/Macroheterocycles, 3, 51–62 (2010).
A. Tulinsky, Ann. N. Y. Acad. Sci., 206, 47–67 (1973).
J. L. Hoard, Ann. N. Y. Acad. Sci., 206, 18–29 (1973).
K. N. Solovyov, L. L. Gladkov, A. S. Starukhin, and S. F. Shkirman, Spectroscopy of Porphyrins: Vibrational States [in Russian], Nauka i Tekhnika, Minsk (1985), pp. 21–27.
A. J. Gordon and R. A. Ford, A Chemist’s Companion, Wiley Interscience, New York (1972).
B. D. Berezin, Coordination Compounds of Porphyrins and Phthalocyanines [in Russian], Nauka, Moscow (1978).
M. Gouterman, in: The Porphyrins, D. Dolphin, ed., Vol. 111, Academic Press, New York (1978), pp. 1–165.
V. A. Kuzmitsky, K. N. Solovyov, and M. P. Tsvirko, in: Porphyrins: Spectroscopy, Electrochemistry, and Application [in Russian], N. S. Enikolopyan, ed., Nauka, Moscow (1987), pp. 7–126.
M. Gouterman, J. Mol. Spectrosc., 6, 138–163 (1961).
G. D. Egorova, K. N. Solovyov, and A. M. Shulga, Zh. Obshch. Khim., 37, 357–361 (1967).
J. D. Keegan, A. M. Stolzenberg, Y.-C. Lu, R. E. Linder, G. Barth, A. Moscowitz, E. Bunnenberg, and C. H. Djerassi, J. Am. Chem. Soc., 104, 4305–4317 (1982).
E. A. Makarova, G. V. Korolyova, O. L. Tok, and E. A. Lukyanets, J. Porphyrins Phthalocyanines, 4, 525–531 (2000).
V. A. Kuzmitsky, E. A. Makarova, P. P. Pershukevich, I. K. Shushkevich, K. N. Solovyov, and V. B. Tusov, Chem. Phys., 298, 1–16 (2004).
Author information
Authors and Affiliations
Corresponding author
Additional information
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 78, No. 2, pp. 171–180, March–April, 2011.
Rights and permissions
About this article
Cite this article
Volkovich, D.I., Gladkov, L.L., Kuzmitsky, V.A. et al. Calculation of the electronic structure and spectra for bacteriochlorophyll analogs. J Appl Spectrosc 78, 155–164 (2011). https://doi.org/10.1007/s10812-011-9441-x
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10812-011-9441-x