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Photoluminescence properties of Jahn–Teller transition-metal ions
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10.1063/1.3223459
/content/aip/journal/jcp/131/12/10.1063/1.3223459
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/12/10.1063/1.3223459

Figures

Image of FIG. 1.
FIG. 1.

PL scheme in a single-coordinate, , configuration diagram, for the excited and ground electronic states. Within a semiclassical description nonradiative de-excitation by multiphonon relaxation is associated with an activation energy (see text for an explanation). The DKR criterion for PL quenching requires the intersection point to be below the vertical excitation point : . Note that although harmonic models are unrealistic to predict real activation energies, nonradiative processes are blocked by increasing . The critical point for the onset of PL quenching corresponds to , or equivalently . Parameters are explained in the text.

Image of FIG. 2.
FIG. 2.

Single-coordinate, , configuration diagram of the parent octahedral and electronic states as a function of the tetragonal normal coordinate . The ground and excited states exhibit a JT coupling and , respectively. Note that the corresponding configurational energy curves have been plotted using electron-phonon coupling constants and with [Eqs. (10)–(13) in text]. The equilibrium geometry is given by and for the ground and excited states, respectively. Vertical arrows represent electronic transitions associated with JT split states in absorption and emission. The ground-state JT energy is given by . Other parameters are explained in text.

Image of FIG. 3.
FIG. 3.

- and -polarized absorption spectra of at 10 K and the corresponding band assignment: , , and (adapted from Ref. 12). The vibrational progression of the first absorption band gives a Huang–Rhys parameter . Within a singlet-to-singlet transition , the DKR parameter is . (Top left) Energy variation of the vibrational component with the derived from the second derivative spectrum shown below. Note the weak anharmonicity of the vibrational mode derived by fitting the vibronic energy to linear and quadratic terms of : , being the vibrational quantum number of the excited state. (Top right) One electron energy level diagram of in and spin-allowed crystal-field transitions. The crystal structure of is shown in the right side.

Image of FIG. 4.
FIG. 4.

Single-coordinate , configuration diagram for the parent octahedral and electronic states as a function of the tetragonal normal coordinate . The ground and excited states exhibit a JT coupling and , respectively. Note that the corresponding configurational energy curves have been plotted using electron-phonon coupling constants and with [Eqs. (22)–(25) in text]. The equilibrium geometry is given by and for the ground and excited states, respectively (see text for explanation). Vertical arrows represent electronic transitions associated with JT split states in absorption and emission. The ground-state JT energy is given by . Other parameters are explained in text.

Image of FIG. 5.
FIG. 5.

Excitation and emission spectra of at 297 K (adapted from Ref. 22). Both bands consist of two Gaussian components according to the energy diagrams shown on both sides of the figure. The energy separation, and , corresponds to the JT-related splitting of the parent octahedral orbitals at the equilibrium geometry of the excited state and to the parent octahedral orbitals at the equilibrium geometry of the ground state , with , respectively, as shown in the energy level diagrams on the top left (emission) and right (excitation). The corresponding equilibrium geometries for the excited and ground states on the basis of the JT effect are also included.

Tables

Generic image for table
Table I.

Spectroscopic parameters for TM ions in different crystals, including the absorption energy and the JT splittings ( and ) derived from the optical spectra given in the reference therein. The last two columns collect the JT-DKR parameter and the PL behavior.

Generic image for table
Table II.

Spectroscopic parameters for TM ions in different crystals, including the absorption energy and the JT splittings ( and ) derived from the optical spectra given in the reference therein. The last two columns collect the JT-DKR parameter and the PL behavior.

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/content/aip/journal/jcp/131/12/10.1063/1.3223459
2009-09-28
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photoluminescence properties of Jahn–Teller transition-metal ions
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/12/10.1063/1.3223459
10.1063/1.3223459
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