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

被引:89
作者
Chandrasekaran, Suryanarayanan [1 ]
Aghtar, Mortaza [1 ]
Valleau, Stephanie [2 ]
Aspuru-Guzik, Alan [2 ]
Kleinekathoefer, Ulrich [1 ]
机构
[1] Jacobs Univ Bremen, Dept Phys & Earth Sci, D-28759 Bremen, Germany
[2] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA
关键词
LIGHT-HARVESTING COMPLEX; MATTHEWS-OLSON COMPLEX; EXCITATION-ENERGY TRANSFER; GREEN SULFUR BACTERIA; MOLECULAR-DYNAMICS; PHOTOSYNTHETIC COMPLEXES; ELECTRONIC-TRANSITIONS; ABSORPTION-SPECTRUM; OPTICAL-PROPERTIES; COHERENCE;
D O I
10.1021/acs.jpcb.5b03654
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Stnclies 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 quantinn 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 lowenergy 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 derisity 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.
引用
收藏
页码:9995 / 10004
页数:10
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