TY - JOUR
T1 - Electron-phonon interactions in CsCdBr3=Yb3+
AU - Hehlen, Markus P.
AU - Kuditcher, Amos
AU - Rand, Stephen C.
AU - Tischler, Michael A.
PY - 1997/10/1
Y1 - 1997/10/1
N2 - Pronounced electron-phonon coupling is observed for the 2F7/2↔2F5/2 4f transitions of Yb3+ doped into CsCdBr3. A comparison of the Raman spectrum and the luminescence excitation sideband accompanying the 2F7/2(0)→2F5/2(2′) crystal-field transition reveals vibrational properties of the [YbBr6] coordination unit that differ markedly from those of the CsCdBr3 host. In particular, the vibronic transition associated with the totally symmetric [YbBr6] stretching mode appears as a very weak feature at 191 cm-1 in the Raman spectrum, whereas the totally symmetric [CdBr6] stretching mode of the CsCdBr3 bulk, which appears as a strong feature at 162.5 cm-1 in the Raman spectrum, is only weakly discernible in the sideband. This is direct evidence for a large contribution from [YbBr6] local modes and a small contribution from bulk modes to the vibronic intensity. The intensity of the local mode is enhanced by approximately a factor of 2 in the Raman spectrum when the laser is tuned into resonance with the 2F7/2(0)→2F5/2(2′) absorption of Yb3+, providing direct confirmation of its assignment. The observation of the first and second members of a Franck-Condon progression for both the local and the bulk totally symmetric modes indicates that a Δ process, rather than an M process, induces the vibronic intensity. Huang-Rhys factors of Slocal=0.010±0.002 and Sbulk=0.15±0.03 were determined from the data, and reflect quite different electron-phonon coupling strengths. These results suggest that multiphonon relaxation of excited electronic states proceeds by the excitation of local modes of [YbBr6] followed by energy transfer to bulk modes of the lattice, possibly through a nonlinear coupling mechanism which is discussed briefly.
AB - Pronounced electron-phonon coupling is observed for the 2F7/2↔2F5/2 4f transitions of Yb3+ doped into CsCdBr3. A comparison of the Raman spectrum and the luminescence excitation sideband accompanying the 2F7/2(0)→2F5/2(2′) crystal-field transition reveals vibrational properties of the [YbBr6] coordination unit that differ markedly from those of the CsCdBr3 host. In particular, the vibronic transition associated with the totally symmetric [YbBr6] stretching mode appears as a very weak feature at 191 cm-1 in the Raman spectrum, whereas the totally symmetric [CdBr6] stretching mode of the CsCdBr3 bulk, which appears as a strong feature at 162.5 cm-1 in the Raman spectrum, is only weakly discernible in the sideband. This is direct evidence for a large contribution from [YbBr6] local modes and a small contribution from bulk modes to the vibronic intensity. The intensity of the local mode is enhanced by approximately a factor of 2 in the Raman spectrum when the laser is tuned into resonance with the 2F7/2(0)→2F5/2(2′) absorption of Yb3+, providing direct confirmation of its assignment. The observation of the first and second members of a Franck-Condon progression for both the local and the bulk totally symmetric modes indicates that a Δ process, rather than an M process, induces the vibronic intensity. Huang-Rhys factors of Slocal=0.010±0.002 and Sbulk=0.15±0.03 were determined from the data, and reflect quite different electron-phonon coupling strengths. These results suggest that multiphonon relaxation of excited electronic states proceeds by the excitation of local modes of [YbBr6] followed by energy transfer to bulk modes of the lattice, possibly through a nonlinear coupling mechanism which is discussed briefly.
UR - http://www.scopus.com/inward/record.url?scp=0000488048&partnerID=8YFLogxK
U2 - 10.1063/1.474851
DO - 10.1063/1.474851
M3 - Article
AN - SCOPUS:0000488048
SN - 0021-9606
VL - 107
SP - 4886
EP - 4892
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 13
ER -