Theoretical Studies of Quantum Dynamics

Using the FPF method, we have carried out accurate path integral simulations of the primary charge separation in bacterial photosynthesis. The process is modeled in terms of three coupled electronic states corresponding to the photoexcited special pair, the reduced accessory bacteriochlorophyll and the reduced bacteriopheophytin of the L branch which interact with a dissipative medium of protein and solvent degrees of freedom. We found that a free energy of the reduced bacteriochlorophyll state about 400 cm$\sp{-1}$ lower than that of the excited special pair, which is associated with a two-step electron transfer mechanism, yields state populations in agreement with experimental results on wild-type and modified reaction centers including the observed temperature dependence. The results are found to be rather stable with respect to reasonable changes of the medium spectral density and the specifics of the nonequilibrium configuration of the photoexcited donor state.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Sim, Eunji

Contributors dc:contributor

• Makri, Nancy

• Physics, General

Language dc:language

eng

Identifier

(MiAaPQ)AAI9737251

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84371