Inductive-resonant theory of nonradiative transitions in lanthanide and transition metal ions (review)

Свешникова, Е. Б.; Ермолаев, В. Л.

doi:10.1134/s0030400x11070186

Cited by 51 publications

(50 citation statements)

References 33 publications

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“…This efficient nonradiative resonant energy transfer from Mn 2+ to Ln 3+ in the CsPbCl3 NCs is ascribled to the strong spectral overlap between the Mn 2+ emission and Ln 3+ absorption, similarly to the case of Mn 2+ or Cr 3+ -Er 3+ codoped insulating matrices. [47][48][49][50][51] These findings reveal that Mn 2+ is a very versatile sensitizer for NIR Ln 3+ emitters with an energy level energetically close to the 4 T1 level of Mn 2+ as discussed further in the text. Figures 3b-d show the PL decay dynamics of Er 3+ emission at 1542 nm, Ho 3+ emission at 986 nm and Nd 3+ emission at 1064 nm in the codoped NCs, respectively.…”

Section: Resultsmentioning

confidence: 58%

Switching on Near-Infrared Light in Lanthanide-doped CsPbCl3 Perovskite Nanocrystals.pdf

Zeng¹,

Locardi

Mara³

et al. 2020

Preprint

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The accessible emission spectral range of lead halide perovskite (LHP) CsPbX3 (X = Cl−, Br−, I−) nanocrystals (NCs) has remained so far limited to wavelengths below 1 μm, corresponding to the emission line of Yb3+, whereas the direct sensitization of other near-infrared (NIR) emitting lanthanide ions is unviable. Herein, we present a general strategy to enable intense NIR emission from Er3+ at ~1.5 μm, Ho3+ at ~1.0 μm and Nd3+ at ~1.06 μm through a Mn2+-mediated energy-transfer pathway. Steady-state and time-resolved photoluminescence studies show that energy-transfer efficiencies of about 39%, 35% and 70% from Mn2+ to Er3+, Ho3+ and Nd3+ are obtained, leading to photoluminescence quantum yields of ~0.8%, ~0.7% and ~3%, respectively. This work provides guidance on constructing energy-transfer pathways in semiconductors and opens new perspectives for the development of lanthanide-functionalized LHPs as promising materials for optoelectronic devices operating in the NIR region.

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Section: Resultsmentioning

confidence: 58%

Switching on Near-Infrared Light in Lanthanide-doped CsPbCl3 Perovskite Nanocrystals.pdf

Zeng¹,

Locardi

Mara³

et al. 2020

Preprint

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“…The τ obs values of YbL are lower than those reported for Yb(III) complexes containing C−H bonds (typically below 50 μs) [2–7] . The rate of the nonradiative deactivation of the Ln(III) excited state is inversely proportional to the distance between the Ln(III) and the C−H bond [22] . According to the crystal structure of YbL, there are methylene and methine C−H bonds with short Yb⋅⋅⋅H distances (3.4–4.4 Å).…”

Section: Resultsmentioning

confidence: 71%

“…[2][3][4][5][6][7] The rate of the nonradiative deactivation of the Ln(III) excited state is inversely proportional to the distance between the Ln(III) and the CÀ H bond. [22] According to the crystal structure of YbL, there are methylene and methine CÀ H bonds with short Yb•••H distances (3.4-4.4 Å). These CÀ H bonds may significantly deactivate the Yb(III) excited state and shorten τ obs in YbL.…”

Section: Luminescence Property Of Yblmentioning

confidence: 99%

Short Radiative Lifetime and Non‐Triplet Sensitization in Near‐Infrared‐Luminescent Yb(III) Complex with Tripodal Schiff Base

et al. 2021

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We prepared Ln(III) (Ln = Eu, Gd, and Yb) complexes with a tripodal Schiff base, tris[2-(5-methylsalicylideneimino)ethyl] amine (H 3 L) and studied their photophysical properties. Upon ligand excitation, YbL showed Yb(III)-centered luminescence in the near-infrared region. While the overall quantum yield (0.60(1)%) of YbL in acetonitrile was moderate among the reported values for Yb(III) complexes, its radiative lifetime (0.33(2) ms) was significantly shorter than those reported previously. We propose that the ligand-to-metal charge-transfer (LMCT) state mediated the sensitization in YbL. The emission and excitation spectra of EuL indicated the participation of the LMCT state in the sensitization. The radiative lifetime (0.84(7) ms) for EuL in the solid state was rather short compared to those of reported Eu(III) complexes. Our results show that the Yb(III) complex with the Schiff base ligand has two features: the short radiative lifetime and the non-triplet sensitization path.

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“…URL: http://www.esmedvedev.orc.ru. omy and astrophysics (Najita et al, 2009;Rothman et al, 2010), overtone-induced chemistry (Crim, 1984(Crim, , 1990(Crim, , 1996Gupta et al, 2010;Hutchinson, 1986;Larsen and Vaida, 2012;Scherer and Zewail, 1987;Takahashi et al, 2008), in studies of intramolecular processes (Fleming et al, 1991;Hippler and Quack, 1996;Portnov et al, 2012), and nonradiative transitions in laser crystals and glasses (Sveshnikova and Ermolaev, 2011).…”

Section: Introductionmentioning

confidence: 99%

Towards understanding the nature of the intensities of overtone vibrational transitions

Medvedev

2012

The Journal of Chemical Physics

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The overtone vibrational transitions, i.e., transitions between states separated by more than one vibrational quantum play important role in many fields of physics and chemistry. The overtone transition is a purely quantum process associated with the so-called dynamical tunneling [Heller, E. J., "The many faces of tunneling," J. Phys. Chem. A 103(49), 10433-10444 (1999)] whose probability is small as compared to the fundamental transition. The transition probability is proportional to the Landau-Lifshitz tunneling factor similar to the Gamov factor in nuclear physics. However, as opposed to the Gamov tunneling, the Landau-Lifshitz tunneling lacks any barrier to tunnel through: Its probability looks as if the system were forced to "dive" under the barrier up to a point where the transition can be performed without any change in momentum, hence with a high probability, and then to "emerge back" in a new state. It follows that the transition probability is associated with the shape of the potential in the classically forbidden region in the same sense as the transition energy is associated with the shape of the potential in the classically allowed region, as implied by the Bohr-Sommerfeld quantization rule, and in the same sense as the probability of the Gamov tunneling is associated with the shape of the potential within the barrier region. As soon as the tunneling character of the transition is recognized, the well-known extreme sensitivity of the overtone intensities to small variations of the fitting function representing the molecular potential [Lehmann, K. K. and Smith, A. M., "Where does overtone intensity come from?" J. Chem. Phys. 93(9), 6140-6147 (1990)] becomes fully understood: Small variations of the potential in the classical region, which do not affect the energy levels significantly, cause large variations in the forbidden region and hence do affect the tunneling factor. This dictates a clear strategy of constructing the potential energy and dipole moment functions (PEF and DMF) capable of explaining the data of vibrational spectroscopy and possessing a predictive power. In this paper, we will show that, for stretching vibrations, knowledge of the inner wall of the PEF is necessary to perform this task. Incorrect behavior of the PEF at extremely small interatomic separations corresponding to energies well above the dissociation limit results in an incorrect rate of the intensity falloff, hence a rapid increase of discrepancies between the calculated and observed intensities with overtone number. Analysis of experimental data on some di- and polyatomic molecules and their interpretations is presented, which shows that neglecting the tunneling nature of overtone transitions does not permit making predictions of the intensities with a known uncertainty. A new approach has to be developed. First of all, an ab initio PEF giving correct energy levels and having correct behavior of the repulsive wall must be constructed; thereafter, an ab initio DMF is invoked to explain the experimental data for lower (obs...

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Inductive-resonant theory of nonradiative transitions in lanthanide and transition metal ions (review)

Cited by 51 publications

References 33 publications

Switching on Near-Infrared Light in Lanthanide-doped CsPbCl3 Perovskite Nanocrystals.pdf

Switching on Near-Infrared Light in Lanthanide-doped CsPbCl3 Perovskite Nanocrystals.pdf

Short Radiative Lifetime and Non‐Triplet Sensitization in Near‐Infrared‐Luminescent Yb(III) Complex with Tripodal Schiff Base

Towards understanding the nature of the intensities of overtone vibrational transitions

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