Influence of Force Fields and Quantum Chemistry Approach on Spectral Densities of BChl a in Solution and in FMO Proteins

• Published in: The journal of physical chemistry. B 2015-08, Vol.119 (31), p.9995-10004
• Main Authors: Chandrasekaran, Suryanarayanan, Aghtar, Mortaza, Valleau, Stéphanie, Aspuru-Guzik, Alán, Kleinekathöfer, Ulrich
• Format: Article
• Language: English
• Subjects: 60 APPLIED LIFE SCIENCES; Bacterial Proteins - chemistry; Bacteriochlorophyll A - chemistry; Density; Dynamical systems; Dynamics; Energy distribution; Excitation; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Light-Harvesting Protein Complexes - chemistry; Models, Molecular; Orbitals; Quantum chemistry; Quantum Theory; solar (photovoltaic), solid state lighting, photosynthesis (natural and artificial), charge transport, optics, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing); Solutions; Spectra
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.5b03654

Studies on light-harvesting (LH) systems have attracted much attention after the finding of long-lived quantum coherences in the exciton dynamics of the Fenna–Matthews–Olson (FMO) complex. In this complex, excitation energy transfer occurs between the bacteriochlorophyll a (BChl a) pigments. Two quantum mechanics/molecular mechanics (QM/MM) studies, each with a different force-field and quantum chemistry approach, reported different excitation energy distributions for the FMO complex. To understand the reasons for these differences in the predicted excitation energies, we have carried out a comparative study between the simulations using the CHARMM and AMBER force field and the Zerner intermediate neglect of differential orbital (ZINDO)/S and time-dependent density functional theory (TDDFT) quantum chemistry methods. The calculations using the CHARMM force field together with ZINDO/S or TDDFT always show a wider spread in the energy distribution compared to those using the AMBER force field. High- or low-energy tails in these energy distributions result in larger values for the spectral density at low frequencies. A detailed study on individual BChl a molecules in solution shows that without the environment, the density of states is the same for both force field sets. Including the environmental point charges, however, the excitation energy distribution gets broader and, depending on the applied methods, also asymmetric. The excitation energy distribution predicted using TDDFT together with the AMBER force field shows a symmetric, Gaussian-like distribution.