banner image
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
A model electronic Hamiltonian to study low-lying electronic states of [Fe(bpy)3]2+ in aqueous solution
Rent this article for


Image of FIG. 1.
FIG. 1.

Definitions of local frame , atom symbols, and partial charges for the bipyridine ligand.

Image of FIG. 2.
FIG. 2.

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.

Image of FIG. 3.
FIG. 3.

(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.

Image of FIG. 4.
FIG. 4.

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.

Image of FIG. 5.
FIG. 5.

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.

Image of FIG. 6.
FIG. 6.

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).

Image of FIG. 7.
FIG. 7.

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).

Image of FIG. 8.
FIG. 8.

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


Generic image for table
Table I.

Properties of optimized [Fe(bpy)3]2+ geometries.

Generic image for table
Table II.

Parameters in the model electronic Hamiltonian.


Article metrics loading...


Full text loading...

This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A model electronic Hamiltonian to study low-lying electronic states of [Fe(bpy)3]2+ in aqueous solution