Modelling the bacterial photosynthetic reaction center.: V.: Assignment of the electronic transition observed at 2200 cm-1 in the special-pair radical-cation as a second-highest occupied molecular orbital to highest occupied molecular orbital transition

Primary charge separation in photoexcited photosynthetic reaction centers produces the radical cation P+ of a bacteriochlorophyll dimer known as the special-pair P. P+ has an intense electronic transition in the vicinity of 1800-5000 cm-1 which is usually assigned to the interchromophore hole-transfer excitation of the dimer radical cation; in principle, this spectrum can give much insight into key steps of the solar-to-electrical energy-conversion process. The extent to which this transition is localized on one-half of the dimer or delocalized over both is of utmost importance; an authoritative deduction of this quantity from purely spectroscopic arguments requires the detailed assignment of the observed high to medium resolution spectra. For reaction centers containing bacteriochlorophylls a or b, a shoulder is observed at 2200 cm-1 on the low-energy side of the main hole-transfer absorption band, a band whose maximum is near 2700 cm-1. Before quantitative analysis of the hole-transfer absorption in these well-studied systems can be attempted, the nature of the processes leading to this shoulder must be determined. We interpret it as arising from an intrachromophore SHOMO to HOMO transition whose intensity arises wholly through vibronic coupling with the hole-transfer band. A range of ab initio and density-functional calculations are performed to estimate the energy of this transition both for monomeric cations and for P+ of Blastochloris viridis, Rhodobacter sphaeroides, Chlorobium limicola, Chlorobium tepidum, Chlamydomonas reinhardtii, Synochocystis S.6803, spinach photosystems I and II, Heliobacillus mobilis, and finally Heliobacterium modesticaldum, with the results found to qualitatively describe the available experimental data. Subsequent papers in this series provide quantitative analyses of the vibronic coupling and complete spectral simulations based on the model developed herein. (C) 2003 American Institute of Physics.