Mn3+ in trigonal bipyramidal coordination: a new blue chromophore.
We show that trivalent manganese, Mn(3+), imparts an intense blue color to oxides when it is introduced at dilution in trigonal bipyramidal coordination. Our optical measurements and first-principles density functional theory calculations indicate that the blue color results from an intense absorption in the red/green region. This absorption is due in turn to a symmetry-allowed optical transition between the valence-band maximum, composed of Mn 3d(x(2)-y(2),xy) states strongly hybridized with O 2p(x,y) states, and the narrow Mn 3d(z(2))-based conduction-band minimum. We begin by demonstrating and explaining the effect using a well-defined prototype system: the hexagonal YMnO(3)-YInO(3) solid solution. We then show that the behavior is a general feature of diluted Mn(3+) in this coordination environment.
Smith
Andrew E
AE
Department of Chemistry, Oregon State University, Corvallis, Oregon 97330-4003, USA.
Mizoguchi
Hiroshi
H
Delaney
Kris
K
Spaldin
Nicola A
NA
Sleight
Arthur W
AW
Subramanian
M A
MA