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A model electronic Hamiltonian to study low-lying electronic states of [Fe(bpy)3]2+ in aqueous solution
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10.1063/1.3684239
/content/aip/journal/jcp/136/6/10.1063/1.3684239
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/6/10.1063/1.3684239

Figures

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

Tables

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.

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/content/aip/journal/jcp/136/6/10.1063/1.3684239
2012-02-14
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A model electronic Hamiltonian to study low-lying electronic states of [Fe(bpy)3]2+ in aqueous solution
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/6/10.1063/1.3684239
10.1063/1.3684239
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