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The Generalized Energy-Based Fragmentation Approach with an Improved Fragmentation Scheme: Benchmark Results and Illustrative Applications

Authors

  • Shugui Hua,

    1. School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, Nanjing University, Hankou Road 22, 210093 Nanjing (P. R. China), Fax: (+86) 25-83686466
    2. College of Life Science and Chemistry, Jiangsu Institute of Education, Beijing west Road 77, 210013 Nanjing (P. R. China)
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  • Wei Li,

    1. School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, Nanjing University, Hankou Road 22, 210093 Nanjing (P. R. China), Fax: (+86) 25-83686466
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  • Prof. Shuhua Li

    Corresponding author
    1. School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, Nanjing University, Hankou Road 22, 210093 Nanjing (P. R. China), Fax: (+86) 25-83686466
    • School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, Nanjing University, Hankou Road 22, 210093 Nanjing (P. R. China), Fax: (+86) 25-83686466
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Abstract

We propose an improved fragmentation scheme for the generalized energy-based fragmentation (GEBF) approach, which improves the accuracy of the GEBF approach in total energy calculations and intermolecular interactions. The main modification is to introduce some two-fragment-centered primitive subsystems, which are neglected in the previous GEBF implementation. Numerical calculations demonstrate that the present GEBF approach can provide more accurate ground-state energies and intermolecular interactions. The present GEBF approach with the M06-2X functional and the cc-pVTZ basis set are employed to investigate the structures and binding energies in two dimeric species, which are related to pseudopolymorphism of a phenyleneethynylene-based π-conjugated molecule. A comparison of the binding free energies in a dimeric species and its corresponding model without C[BOND]H⋅⋅⋅F contacts reveal that the substitution of fluorine atoms weakens the binding of monomers in the dimeric species formed by intermolecular O[BOND]H⋅⋅⋅O hydrogen bonds, but strengthens the binding in the dimer formed by the π–π stacking interaction. Therefore, the C[BOND]H⋅⋅⋅F contacts in these two dimeric species are demonstrated to play a less significant role.

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