Spectral shift mechanisms of chlorophylls in liquids and proteins

Origins of non-excitonic spectral shifts of chlorophylls that can reach -1,000 cm(-1) in pigment-protein complexes are actively debated in literature. We investigate possible shift mechanisms, basing on absorption and fluorescence measurements in large number of liquids. Transition wavelength in solvent-free state was estimated (±2 nm) for chlorophyll a (Chl a, 647 nm), Chl b (624 nm), bacteriochlorophyll a (BChl a, 752 nm), and pheophytines. The dispersive-repulsive shift is a predominating mechanism. It depends on polarizability difference between the ground and the excited state Δα and the Lorenz-Lorentz function of refractive index of solvent (n). The approximate (± 2Å(3)) increase of polarizability Δα is close to 15Å(3) for S(1) bands of Chl a, BChl a, and BPheo a, slightly larger for Chl b (18Å(3)), and less for Pheo a (11Å(3)). The effect of solvent polarity, expressed in terms of static dielectric permittivity (ε) is relatively minor, but characteristic for different pigments and transitions. Remarkably, maximum influence of ε on S(1) band of BChl a is less (-20 ± 10 cm(-1)) than that for Chl a (-50 ± 10 cm(-1)), and not correlated with dipole moment changes on excitation Δμ (∼2D and 0.1 ± 0.1D, respectively). Hydrogen bonding in protic solvents produces red shifts in Chl a (-60 cm(-1)) and BChl a (-100 cm(-1)), but not in Chl b. Second axial ligand of BChl a has no influence on the S(1) band, whereas the S(2) transition suffers a -400 to -600 cm(-1) down shift. Aromatic character of solvent is responsible for a ∼-100 cm(-1) red shift of both Q transitions in BChl a. The S(1) bands in chlorophylls are relatively insensitive with respect to dielectric properties and specific solvation. Therefore, nontrivial mechanisms, yielding large site-energy shifts are expected in photosynthetic chlorophyll-proteins.