New Insights in 4f 12 5d 1 Excited States of Tm 2+ through Excited State Excitation Spectroscopy

de Jong, Mathijs; Biner, Daniel; Krämer, Karl; Barandiarán, Zoila; Seijo, Luis; Meijerink, Andries (2016). New Insights in 4f 12 5d 1 Excited States of Tm 2+ through Excited State Excitation Spectroscopy. The journal of physical chemistry letters, 7(14), pp. 2730-2734. American Chemical Society 10.1021/acs.jpclett.6b00924

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Optical excitation of ions or molecules typically leads to an expansion of the
equilibrium bond lengths in the excited electronic state. However, for 4fn−15d1 excited states in
lanthanide ions both expansion and contraction relative to the 4fn ground state have been reported,
depending on the crystal field and nature of the 5d state. To probe the equilibrium distance offset
between different 4fn−15d1 excited states, we report excited state excitation (ESE) spectra for Tm2+
doped in CsCaBr3 and CsCaCl3 using two-color excited state excitation spectroscopy. The ESE
spectra reveal sharp lines at low energies, confirming a similar distance offset for 4fn−15d(t2g)1 states.
At higher energies, broader bands are observed, which indicate the presence of excited states with a
different offset. On the basis of ab initio embedded-cluster calculations, the broad bands are
assigned to two-photon d−d absorption from the excited state. In this work, we demonstrate that
ESE is a powerful spectroscopic tool, giving access to information which cannot be obtained
through regular one-photon spectroscopy.

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