Electronic and spectral properties of ametal-organic super container molecule by single point DFT

Sapp, Wendi; Erck, Adam; Wang, Zenqiang; Kilin, Dmitri S.

doi:10.1080/00268976.2015.1076899

Cited by 3 publications

(6 citation statements)

References 17 publications

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“…Diluted magnetic oxides and semiconductors, such as cobalt-doped titania and manganese-doped zinc oxide or cadmium selenide, in the form of nanocrystals and quantum dots, represent different patterns of ligand arrangement and crystal-field splitting and exhibit new spectral features contributed by the dopant TM ions . Approaches and results of this work have potential for further application in identification of mechanisms for basic photoinduced processes in magnetically doped quantum dots or molecular magnets for information storage applications. ,, Magnetic molecular crystals and magnetic metalorganic frameworks , also exhibit variable coordination patterns of TM ions to neighboring ligands that may allow the design of new spin-crossover materials.…”

Section: Discussionmentioning

confidence: 99%

Relationship between Site Symmetry, Spin State, and Doping Concentration for Co(II) or Co(III) in β-NaYF₄

Berry

May

et al. 2016

J. Phys. Chem. C

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Magnetic dopants provide versatile tunability of properties for transparent host matrix materials, semiconductors, and nanostructured materials. The relationship between doping concentration, site symmetry, crystal-field splitting, and spin state for Co(II) and Co(III) doped in hexagonal-phase NaYF 4 crystals and nanocrystals was investigated in a spin-polarized density functional theory approach. With decreasing dopant concentrations, the geometry of the Co(II) fluoride nearest-neighbor coordination changes from approximately square pyramidal to square planar to cubic before converging to pentagonal bipyramidal coordination. A transition from low-spin to high-spin was observed, accompanying the geometry transformation from square planar to cubic, which is consistent with expectations from basic crystal-field theory. Magnetic ordering of adjacent ions was found to have little influence on this spin-transition process. For Co(III), decreasing concentration resulted in a geometry transformation from approximately octahedral to a convergent square pyramidal coordination. A low-spin configuration was retained at all Co(III) doping concentrations. This work presents a strategy for the design of spin-crossover materials by manipulating the doping concentration of the spin-crossover center.

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Section: Discussionmentioning

confidence: 99%

Relationship between Site Symmetry, Spin State, and Doping Concentration for Co(II) or Co(III) in β-NaYF₄

Berry

May

et al. 2016

J. Phys. Chem. C

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“…351,352 Cobaltbased polyoxometalates have been applied to energy systems such as the redox couple in dye-sensitized solar cells. 43,349,[353][354][355][356][357][358][359] A number of other transition metalbased polyoxometalates have been investigated, such as silver-containing polyoxometalates, 226,[360][361][362][363][364][365] zinccontaining polyoxometalates. 366 polyoxotantalate, [367][368][369][370][371][372][373][374][375][376][377][378][379][380][381][382][383][384] ruthenium-containing polyoxometalates, [385][386][387] coppercontaining polyoxometalates, [388][389][390] chromium-containing polyoxometalates, 391 and polyoxoaurates [392][393]…”

Section: Polyoxopalladatesmentioning

confidence: 99%

“…“Polyoxoiron” is rarely obtained, but the iron element is frequently introduced into polyoxometalates for various energy applications; for example, it has been employed to enhance the ZnO‐based solar cell performance via the construction of a metal‐organic framework owing to the excellent electron‐separation properties . Cobalt‐based polyoxometalates have been applied to energy systems such as the redox couple in dye‐sensitized solar cells . A number of other transition metal‐based polyoxometalates have been investigated, such as silver‐containing polyoxometalates, zinc‐containing polyoxometalates .…”

Section: Other Polyoxometalatesmentioning

confidence: 99%

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

Zhang

Chen

2020

Int J Energy Res

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Summary Polyoxometalates could be viewed as the molecular counterpart of the metal oxides, which are essential ingredients for various energy conversion and storage applications. In this manuscript, we review the progress of engineering functional polyoxometalates toward energy applications, focusing on, but not limited to, polyoxotitanate, polyoxotungstate, and polyoxomolybdate. These polyoxometalates are considered to be promising candidates for dye‐sensitized solar cell, perovskite solar cell, lithium‐ion battery, lithium‐sulfur battery, supercapacitor, and water‐splitting system. We believe advanced energy devices with better performance could be derived from further engineering the polyoxometalates owing to their molecular design flexibility.

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“…Spin-unrestricted electronic structure was found useful in describing ferromagnetic materials, including TiO 2 doped by transition metals, as well as vanadium, and TiO 2 with oxygen vacancy converting Ti 4+ to Ti 3+ resulting in a local magnetic moment at Ti 3+ ions . The success of using the ground state spin polarized electronic properties has been shown in adequate predicting electronic configurations matching Russell–Saunders terms of lanthanide-doped laser crystals , and properties of metal–organic frameworks . This article uses the spin-polarized DFT ground state electron computations as a basis for studying spin-unrestricted nonadiabatic dynamics.…”

Section: Introductionmentioning

confidence: 99%

“…32 The success of using the ground state spin polarized electronic properties has been shown in adequate predicting electronic configurations matching Russell−Saunders terms of lanthanide-doped laser crystals 33,34 and properties of metal−organic frameworks. 35 This article uses the spin-polarized DFT ground state electron computations as a basis for studying spin-unrestricted nonadiabatic dynamics.…”

Section: Introductionmentioning

confidence: 99%

Spin Unrestricted Excited State Relaxation Study of Vanadium(IV)-Doped Anatase

2016

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Atomistic modeling of light driven electron dynamics are important in studies of photoactive materials. Spin-resolved electronic structure calculations become necessary when dealing with transition metal, magnetic, and even some carbon materials, intermediates, and radicals. An approximate treatment can be pursued in the basis of spincollinear density functional theory. Most transition-metal compounds exhibit open shell nonsinglet configurations, necessitating special treatment of electrons with α/β spin projections. By separate treatment of electronic states with the α/β spin components one is able to describe a broader range of materials, identify new channels of relaxation and charge transfer, and provide knowledge for rational design of new materials in solar energy harvesting and information storage. For this methodology, named spin-resolved electron dynamics, spin-polarized DFT is used as the basis to implement nonadiabatic molecular dynamics. At ambient temperatures, the thermal lattice vibrations results in orbital and energy fluctuations with time. Nonadiabatic couplings are then calculated, which control the dissipative dynamics of the spin resolved density matrix. Different initial excitations are then analyzed and used to calculate relaxation dynamics. Spin-resolved electronic dynamics approach (SREDA) is applied to study vanadium(IV) substitutionally doped bulk anatase in a doublet ground state. The results show that a difference in the electronic structure for α and β spin components determines consequences in optical excitations and electronic dynamics pathways experienced by electrons with α and β spin projections. Specifically, the lone occupied V 3d α-orbital increases the range of absorption and defines the rates and pathways of relaxation for both holes and electrons with α-spin projection. Optical excitations involving occupied V 3d α-orbital are responsible for IR-range absorption, followed by nonradiative relaxation. Certain transitions involving orbitals of α-spin component occur in the visible range and induce localization of a negative charge on the V ion for an extended time period. The slower nonradiative relaxation rate of α-excitations is rationally explained as a consequence of difference of electronic structure for α and β spin projections and specific pattern of energy levels contributed by doping. Specifically, excitations involving orbitals with α-projection of spin experience transitions through larger subgaps in the conduction band compared to the ones experienced by similar excitations involving orbitals with β-projection of spin. It is anticipated that this methodology can be broadly implemented on multiple applications of transition metal based materials, including optoelectronics, information storage, laser crystals, dyes, photovoltaic materials, and metal oxides for photoelectrochemical water splitting.

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Electronic and spectral properties of ametal-organic super container molecule by single point DFT

Cited by 3 publications

References 17 publications

Relationship between Site Symmetry, Spin State, and Doping Concentration for Co(II) or Co(III) in β-NaYF₄

Relationship between Site Symmetry, Spin State, and Doping Concentration for Co(II) or Co(III) in β-NaYF₄

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

Spin Unrestricted Excited State Relaxation Study of Vanadium(IV)-Doped Anatase

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Electronic and spectral properties of ametal-organic super container molecule by single point DFT

Cited by 3 publications

References 17 publications

Relationship between Site Symmetry, Spin State, and Doping Concentration for Co(II) or Co(III) in β-NaYF4

Relationship between Site Symmetry, Spin State, and Doping Concentration for Co(II) or Co(III) in β-NaYF4

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

Spin Unrestricted Excited State Relaxation Study of Vanadium(IV)-Doped Anatase

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Product

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Relationship between Site Symmetry, Spin State, and Doping Concentration for Co(II) or Co(III) in β-NaYF₄

Relationship between Site Symmetry, Spin State, and Doping Concentration for Co(II) or Co(III) in β-NaYF₄