Intervalence Band Stark Effect of the Special Pair Radical Cation in Bacterial Photosynthetic Reaction Centers

Autor: Thomas P. Treynor, Steven S. Andrews, Steven G. Boxer
Rok vydání: 2003
Předmět:
Zdroj: The Journal of Physical Chemistry B. 107:11230-11239
ISSN: 1520-5207
1520-6106
DOI: 10.1021/jp035039f
Popis: The Stark spectrum of the intervalence band of the special pair radical cation in bacterial photosynthetic reaction centers is presented. This spectrum, centered at 2600 cm-1, is modeled using a general treatment of intervalence band Stark effects based on a two-state vibronic coupling model of mixed-valency. The observed line shape can be predicted using values for the electronic coupling, driving force, and reorganization energy along a single antisymmetric mode as derived from previous measurements. The model can be used to estimate the difference between the electric dipole moments of the two hole-localized electronic states of a mixed-valence complex, ΔμCT, even if the dipole strength of its IVB is unknown or affected by intensity borrowing by other electronic transitions. We determine the value of ΔμCT to be 33 ± 5 D/f for the special pair radical cation in wild-type Rhodobacter sphaeroides reaction centers, where f is the scalar approximation to the local field correction tensor. This value of ΔμCT...
Databáze: OpenAIRE