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Generalized Energy-Based Fragmentation Approach for Localized Excited States of Large Systems
Wei Li1, Yunzhi Li1, Ruochen Lin1
1Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, People's Repubic of China.
Abstract:
We have extended the generalized energy-based fragmentation (GEBF) approach to localized excited states of large systems. In this approach, the excited-state energy of a large system could be expressed as the combination of the excited-state energies of "active subsystems", which contains the chromophore center, and the ground-state energies of "inactive subsystems". The GEBF approach has been implemented at the levels of time-dependent density functional theory (TDDFT) and approximate coupled cluster singles and doubles (CC2) method. Our results show that GEBF-TDDFT can reproduce the TDDFT excitation energies and solvatochromic shifts for large systems and that GEBF-CC2 could be used to validate GEBF-TDDFT result (with different functionals). The GEBF-TDDFT method is found to be able to provide satisfactory or reasonable descriptions on the experimental solvatochromic shifts for the n → π* transitions of acetone in various solutions, and the lowest π → π* transitions of pyridine and uracil in aqueous solutions.
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