Charge delocalization in the special-pair radical cation of mutant reaction centers of Rhodobacter sphaeroides from Stark spectra and nonadiabatic spectral simulations.
Stark and absorption spectra for the hole-transfer band of the bacteriochlorophyll special pair in the wild-type and L131LH, M160LH, and L131LH/M160LH mutants of the bacterial reaction center of Rhodobacter sphaeroides are presented, along with extensive analyses based on nonadiabatic spectral simulations. Dramatic changes in the Stark spectra are induced by the mutations, changes that are readily interpreted in terms of the redox-energy asymmetry and degree of charge localization in the special-pair radical cation. The effect of mutagenesis on key properties such as the electronic coupling within the special pair and the reorganization energy associated with intervalence hole transfer are determined for the first time. Results for the L131LH and M160LH/L131LH mutants indicate that these species can be considered as influencing the special pair primarily through modulation of the redox asymmetry, as is usually conceptualized, but M160LH is shown to develop a wide range of effects that can be interpreted in terms of significant mutation-induced structural changes in and around the special pair. The nonadiabatic spectra simulations are performed using both a simple two-state 1-mode and an extensive four-state 70-mode model, which includes the descriptions of additional electronic states and explicitly treats the major vibrational modes involved. Excellent agreement between the two simulation approaches is obtained. The simple model is shown to reproduce key features of the Stark effect of the main intervalence transition, while the extensive model quantitatively reproduces most features of the observed spectra for both the electronic and the phase-phonon regions, thus giving a more comprehensive description of the effect of the mutations on the properties of the special-pair radical cation. These results for a series of closely related mixed-valence complexes show that the Stark spectra provide a sensitive indicator for the properties of the mixed-valence complexes and should serve as an instructive example on the application of nonadiabatic simulations to the study of mixed-valence complexes in general as well as other chemical systems akin to the photosynthetic special pair.
Kanchanawong
Pakorn
P
Biophysics Program and Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA.
Dahlbom
Mats G
MG
Treynor
Thomas P
TP
Reimers
Jeffrey R
JR
Hush
Noel S
NS
Boxer
Steven G
SG
D000042:Absorption; D002412:Cations; D003198:Computer Simulation; D019281:Dimerization; D004563:Electrochemistry / Q000379:methods; D004581:Electronics; D004583:Electrons; D006860:Hydrogen Bonding; D016297:Mutagenesis, Site-Directed; D009154:Mutation; D010084:Oxidation-Reduction; D012242:Rhodobacter sphaeroides / Q000235:genetics*; D013053:Spectrophotometry / Q000379:methods*; D017550:Spectroscopy, Fourier Transform Infrared; D013816:Thermodynamics
D002412:Cations