Definitions of local frame , atom symbols, and partial charges for the bipyridine ligand.
Potential energy curves along the linearly interpolated path between the LS and HS geometries obtained by DFT calculations. The horizontal axis displays Fe−N distance; the linearly interpolated path includes other geometric changes of the complex, such as bond lengths and angles. Results from the model Hamiltonian and DFT calculations are shown by lines and circles, respectively.
(a) Comparisons between normal-mode frequencies of DFT and model Hamiltonian. (b) Inner product of normal-mode vectors, , with respect to normal-mode frequencies of the model Hamiltonian. In both figures, low frequencies up to 1000 cm−1 are shown for clarity.
Potential energy curves of several d−d states along the same linearly interpolated path as shown in Fig. 2. Assignment of electronic states is given by irreducible representation of the D 3 (O h ) point group. Solid, dashed, and dashed-dotted lines denote singlet, triplet, and quintet states, respectively. Energy origin is set to the minimum energy point of the LS (1 A 1) state.
Distributions of (a) Fe−N bond length, (b) C2− bond length, (c) N−Fe−N′ angle, and (d) N−C2−−N′ dihedral angle of the [Fe(bpy)3]2+ complex in aqueous solution. Solid and dashed lines denote singlet (LS) and quintet (HS) results, respectively.
Radial distribution functions of (a) Fe−O and (b) Fe−H for singlet (LS) state (solid), quintet (HS) state (dashed), and the pseudoatom (dashed-dotted).
Ratio of hydrogen and oxygen coordination numbers, N H/N O, with respect to the distance from the Fe2+ ion for the singlet (LS) state (solid), quintet (HS) state (dashed), and the pseudoatom (dashed-dotted).
A representative first solvation structure within 6.3 Å from Fe2+ (green) sampled from a trajectory for the HS state. Red, white, cyan, and blue balls represent oxygen, hydrogen, carbon, and nitrogen atoms, respectively. The figure was created using the VMD program.56
Properties of optimized [Fe(bpy)3]2+ geometries.
Parameters in the model electronic Hamiltonian.
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