Excited states of chlorophyll a and b in solution by time-dependent density functional theory

The ground state and excited state electronic properties of chlorophyll (Chl) a and Chl b in diethyl ether, acetone, and ethanol solutions are investigated using quantum mechanical and molecular mechanical calculations with density functional theory (DFT) and time-dependent DFT (TDDFT). Although the DFT/TDDFT methods are widely used, the electronic structures of molecules, especially large molecules, calculated with these methods are known to be strongly dependent on the functionals and the parameters used in the functionals. Here, we optimize the range-separated parameter, mu, of the CAM-B3LYP functional of Chl a and Chl b to reproduce the experimental excitation energy differences of these Chl molecules in solution. The optimal values of mu for Chl a and Chl b are smaller than the default value of mu and that for bacteriochlorophyll a, indicating the change in the electronic distribution, i.e., an increase in electron delocalization, within the molecule. We find that the electronic distribution of Chl b with an extra formyl group is different from that of Chl a. We also find that the polarity of the solution and hydrogen bond cause the decrease in the excitation energies and the increase in the widths of excitation energy distributions of Chl a and Chl b. The present results are expected to be useful for understanding the electronic properties of each pigment molecule in a local heterogeneous environment, which will play an important role in the excitation energy transfer in light-harvesting complex II.& nbsp;Published under an exclusive license by AIP Publishing.

Automated summary

This study investigates the electronic properties of chlorophyll in different solvents using quantum mechanical and molecular mechanical calculations. By optimizing the parameters of the functional, the experimental results were successfully reproduced, showing changes in the electronic distribution within the molecule. Furthermore, it was observed that the polarity of the solvent and hydrogen bonding affect the excitation energy and its distribution.