On the Absorption Spectra of Complex Ions. I

Tanabe, Yukito; Sugano, Shigeru

doi:10.1143/jpsj.9.753

Cited by 2,006 publications

(632 citation statements)

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“…The Cr 3+ ion shows two kinds of luminescence depending on the crystal field strength of the host lattice, namely, sharp luminescence lines due to the 2 E¼ 4 A 2 (R-line) transitions in a strong crystal-field host and a broad luminescence band due to the 4 T 2 ¼ 4 A 2 transition in a weak crystal-field host. The sharp R-line luminescence is due to the 2 E excited state, which has a small dependence on ligand field strength (Dq), which is well characterized by the shape of the TanabeSugano diagram for 3d 3 electronic configuration in a 6-fold symmetry site 34) shown in Fig. 2 activated phosphors can be described quantitatively, by the small values for both B and the Racah parameter C in this host.…”

Section: )5)mentioning

confidence: 84%

Red to near-infrared persistent luminescence in transition metal ion activated phosphors

Katayama

2017

J. Ceram. Soc. Japan

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Red-to-near infrared persistent phosphors have attracted great attention because they are promising candidates for in vivo imaging. However, for most of the persistent phosphors that are activated only by ultraviolet (UV) light, the detection time is limited because persistent luminescence decays with time and UV excitation cannot be repeated due to the opacity of living tissues to UV radiation. Therefore, we have developed persistent phosphors with perovskite and garnet structures, which show 1) persistent luminescence at an optimum wavelength with high transparency for living tissue, 2) with brighter and longer persistent luminescence, and 3) with an additional function leading to long-term in vivo imaging capability.

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Section: )5)mentioning

confidence: 84%

Red to near-infrared persistent luminescence in transition metal ion activated phosphors

Katayama

2017

J. Ceram. Soc. Japan

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“…LF excitations involve only nominal Ni 3d orbitals and correspond to electronic transitions from the 3 A 2g (e g ,t 2g ) 10 (t 2g * ) 6 (e g *) 2 ground state to the final states of the (e g ,t 2g ) 10 (t 2g * ) 6−n (e g *) 2+n (n = 1, 2) configurations. They determine the optical properties of the complex in the UV−visible spectral region.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…They determine the optical properties of the complex in the UV−visible spectral region. CT excitations involve the nominal water orbitals and correspond to transitions from 3 A 2g (e g ,t 2g ) 10 (t 2g * ,e g *) 8 to states of the (e g ,t 2g ) 9 (t 2g * ,e g *) 9 configuration.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering

et al. 2013

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Bonding of the Ni 2+ (aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d−3d electron correlation interactions in the Ni 2+ (aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d−3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV−vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra. ■ INTRODUCTION3d transition metals in aqueous solution are interesting from a fundamental point of view as their hexaaqua complexes [M(H 2 O) 6 ] n+ represent the archetype of Werner complexes with coordinative bonding in octahedral symmetry. 1 Considering hydrogen bonding between the various coordination spheres of water molecules, they could even be regarded as chelate complexes, 2 and new insight into their electronic structure could help understanding the interplay of bonding, structure, and dynamics in these complexes. This in turn forms the basis for understanding their thermodynamic properties and reactivity, having implications for modeling and understanding phenomena ranging from water exchange reactions 3,4 to photochemical processes 5 and atmospheric liquid chemistry of 3d transition-metal ions in solution. 6 While the structure of 3d transition metal (TM) ions and their complexes in aqueous solution can be addressed experimentally with numerous scattering and spectroscopic methods, 7 bonding can be assessed with a limited set of spectroscopic tools among which, historically, UV−vis spectroscopy has played a dominant role. Complementing such experimental results and due to the strongly polarized character of the coordinate bond, ligand-field theory 8,9 can be successfully applied to hexaaqua complexes. In particular, the dependence of the ligand-field (LF) state energies on ligand-field strength and 3d−3d Coulomb interactions for all 3d n complexes were first calculated by Tanabe and Sugano in their seminal work from 1954. 10,11 The low-energy electronic excited state spectrum of a typical TM coordination complex can thus be described by, with increasing photon energy, the LF excitations, followed by the charge-transfer (CT) and ligand-centered excitations. At present, the excitations to LF states of octahedral TM complexes are very well understood at the semiempirical level of ligand-field theory. Today, ab ini...

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“…Em simetria octaédrica, o desdobramento dos níveis de energia da configuração eletrônica d 8 é descrito pelo diagrama de Tanabe-Sugano [17], mostrado na Fig. 2.…”

Section: Resultsunclassified

Fotoluminescência em amostras policristalinas de galato de magnésio dopado com Ni2+

et al. 2006

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INTRODUÇÃOÍons de metais de transição quando introduzidos como impurezas substitucionais em materiais isolantes hospedeiros podem apresentar largas bandas de absorção e de luminescência no visível e no infravermelho próximo. As propriedades luminescentes dos metais de transição são úteis para diversas aplicações, que variam de materiais ativos para laser de estado sólido a temperatura ambiente até a fabricação de folhas de papel especial [1,2]

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On the Absorption Spectra of Complex Ions. I

Cited by 2,006 publications

References 6 publications

Red to near-infrared persistent luminescence in transition metal ion activated phosphors

Red to near-infrared persistent luminescence in transition metal ion activated phosphors

From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering

Fotoluminescência em amostras policristalinas de galato de magnésio dopado com Ni2+

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On the Absorption Spectra of Complex Ions. I

Cited by 2,006 publications

References 6 publications

Red to near-infrared persistent luminescence in transition metal ion activated phosphors

Red to near-infrared persistent luminescence in transition metal ion activated phosphors

From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni2+ in Aqueous Solution with Resonant Inelastic X-ray Scattering

Fotoluminescência em amostras policristalinas de galato de magnésio dopado com Ni2+

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From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering