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Influence of the protein and DFT method on the broken‐symmetry and spin states in nitrogenase

Cao, Lili (Department of Theoretical Chemistry, Lund University, Chemical Centre, P. O. Box 124, SE‐22100, Lund, Sweden ) ; Ryde, Ulf (Department of Theoretical Chemistry, Lund University, Chemical Centre, P. O. Box 124, SE‐22100, Lund, Sweden ) ;
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    Abstract The enzyme nitrogenase contains a complicated MoFe 7 CS 9 cofactor with 35 possible broken‐symmetry (BS) states. We have studied how the energies of these states depend on the geometry, the surrounding protein, the DFT functional and the basis set, studying the resting state, a one‐electron reduced state and a protonated state. We find that the effect of the basis set is small, up to 11 kJ/mol. Likewise, the effect of the surrounding protein is restricted, up to 10 and 7 kJ/mol for the electrostatic and van der Waals energy terms. Single‐point energies calculated on a single geometry give a good correlation ( R 2 = 0.92‐0.98) to energies calculated after geometry optimization, but some BS states may be disfavored by up to 37 kJ/mol. A change from the pure TPSS functional to the hybrid B3LYP functional may change the relative energies by up to 58 kJ/mol and the correlation between the two results is only 0.57‐0.72. Both functionals agree that BS7 is the most stable BS state and that the ground spin state is the quartet for the resting state and the quintet for the reduced state. With the TPSS functional, the BS6 state is the second most stable state, always at least 21 kJ/mol less stable than the BS7 state. However, with the B3LYP functional, BS10 is the second most stable state and for the protonated state it comes close in energy. Based on these results, we suggest a procedure how to consider the 35 BS states in future investigations of the nitrogenase reaction mechanism.


  • 주제어

    basis set .   broken‐symmetry density functional theory .   DFT functional .   nitrogenase .   QM/MM.  

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