Mix and (Mis)match: further studies of the electronic structure and mixed-valence characteristics of 1,4-diethynylbenzene-bridged bimetallic complexes

2020 ◽  
Vol 49 (28) ◽  
pp. 9835-9848
Author(s):  
Parvin Safari ◽  
Stephen A. Moggach ◽  
Paul J. Low
Keyword(s):  
Electronic Structure ◽  
Ground State ◽  
Mixed Valence ◽  
Bimetallic Complexes ◽  
Redox Processes ◽  
Infra Red ◽  
Donor Acceptor ◽  
The One

Infra-red spectroelectrochemical studies of [{Cp′(CO)xM′}(μ-CCC6H4CC){M(PP)Cp′}]n+ [n = 0, 1] illustrate limited ground-state interactions in these donor–acceptor compounds and the localised nature of the one-electron redox processes.

scholarly journals Inversion of donor–acceptor roles in photoinduced intervalence charge transfers

2019 ◽  
Vol 55 (53) ◽  
pp. 7659-7662 ◽  
Author(s):  
Bruno M. Aramburu-Trošelj ◽  
Paola S. Oviedo ◽  
Ivana Ramírez-Wierzbicki ◽  
Luis M. Baraldo ◽  
Alejandro Cadranel
Keyword(s):  
Electron Donor ◽  
Electron Acceptor ◽  
Ground State ◽  
Mixed Valence ◽  
Donor Acceptor

Upon MLCT photoexcitation, {(tpy)Ru} becomes the electron acceptor in the mixed valence {(tpy˙−)RuIII−δ-NC-MII+δ} moiety, reversing its role as the electron donor in the ground-state mixed valence analogue.

121Sb NMR and SCF-MS-Xα Studies of Quadrupole Interaction and The Electronic Structure of Mixed-Valence Compound, Cs2SbCl6

1996 ◽  
Vol 51 (5-6) ◽  
pp. 672-676 ◽  
Author(s):  
Takahiro Ueda ◽  
Nobuo Nakamura
Keyword(s):  
Electronic Structure ◽  
Charge Transfer ◽  
Ground State ◽  
Mixed Valence ◽  
Quadrupole Coupling Constant ◽  
Coupling Constant ◽  
Nmr Spectrum ◽  
Quadrupole Coupling ◽  
Mixed Valence Compound ◽  
Complex Anions

Cs2SbCl6 is known as a typical mixed-valence compound. It crystallizes into a tetragonal space group I41/amd and contains two different complex anions, Sb(III)Cl3-6 and Sb(V)Cl-6 . The dark blue color of this compound has been considered to originate from a charge transfer between the above two anions. In order to study the electronic structure of these complex anions and the existence of charge transfer between them we measured the 121Sb NMR spectrum and carried out molecular orbital calculations on the electronic states of these anions. The 121Sb NMR spectrum consists of two peaks at 0 and 30 kHz which can be assigned to the central transition of 121Sb in Sb(V)Cl-6 and Sb(III)Cl3-6 , respectively. The line shape analyses of the spectra led to nuclear quadrupole coupling constants of nearly zero for Sb(V)Cl-6 and 4.9 ± 0.5 MHz for Sb(III)Cl3-6 at room temperature. The quadrupole coupling constant of 121Sb(III) decreases steadily on heating. The calculations of the electronic ground state energies of both anions were calculated by the MS-Xα molecular orbital method. The calculated charge-transfer band from the A1g state of Sb(III)Cl3-6 to the A1g state of Sb(V)Cl-6 appears at 610 nm and can account for the experimental electronic spectrum, the calculated quadrupole coupling constant in Sb(III)Cl3-6 however is far larger than the experimental one. The contribution of the charge-transferred state to the ground state is negligible and so the temperature dependence of the quadrupole coupling constant of 121Sb(III) is attributed to an anisotropic thermal expansion of the compound.

Electronic Structure and Photoemission in Plutonium Chalcogenides

2008 ◽  
Vol 1104 ◽  
Author(s):  
Alexander Shick ◽  
Ladislav Havela ◽  
Thomas Gouder
Keyword(s):  
Experimental Data ◽  
Electronic Structure ◽  
Ground State ◽  
Mixed Valence ◽  
Mean Field ◽  
Photoelectron Spectra ◽  
Magnetic Ground State ◽  
Good Agreement

AbstractThe electronic structure of Pu chalcogenides is investigated making use of static around-mean-field LDA+U and dynamical LDA+HIA (Hubbard-I) methods. The LDA+U calculations provide correct non-magnetic ground state for PuX (X = S, Se, Te) with 5f-manifold non-integer filling (∼5.6(PuS)-5.7(PuTe)). This is an indication of a mixed valence ground state which is a combination of f5 and f6 multiplets. The photoelectron spectra are calculated in good agreement with experimental data. The 5f-manifold three-peaks feature near EF is well reproduced by LDA+HIA, and follows from mixed valence character of the ground state.

scholarly journals Two-term expansion of the ground state one-body density matrix of a mean-field Bose gas

2021 ◽  
Vol 60 (3) ◽  
Author(s):  
Phan Thành Nam ◽  
Marcin Napiórkowski
Keyword(s):  
Density Matrix ◽  
Ground State ◽  
Mean Field ◽  
Interaction Strength ◽  
Bose Gas ◽  
Body Density ◽  
The Mean ◽  
The One ◽  
Mean Field Regime ◽  
Number Of Particles

AbstractWe consider the homogeneous Bose gas on a unit torus in the mean-field regime when the interaction strength is proportional to the inverse of the particle number. In the limit when the number of particles becomes large, we derive a two-term expansion of the one-body density matrix of the ground state. The proof is based on a cubic correction to Bogoliubov’s approximation of the ground state energy and the ground state.

scholarly journals Electronic Structure Study of Divanadium Complexes with Rigid Covalent Coordination: Potential Molecular Qubits with Slow Spin Relaxation

2021 ◽  
Author(s):  
Stephen Sproules
Keyword(s):  
Electronic Structure ◽  
Spin Relaxation ◽  
Ground State ◽  
Electronic Structures ◽  
Structure Study ◽  
Ligand Shell

The electronic structures of homovalent [V2(μ-S2)2(R2dtc)4] (R = Et, iBu) and mixed-valent [V2(μ-S2)2(R2dtc)4]+ are reported here. The soft-donor, eight-coordinate ligand shell combined with the fully delocalised ground state provides a...

Magnetic Ground State and Electronic Structure Calculations of PbMnO3 Using DFT

2014 ◽  
Vol 895 ◽  
pp. 420-423 ◽  
Author(s):  
Sathya Sheela Subramanian ◽  
Baskaran Natesan
Keyword(s):  
Electronic Structure ◽  
Band Structure ◽  
Fermi Level ◽  
Ground State ◽  
Density Functional ◽  
Electronic Structure Calculations ◽  
Magnetic Ground State ◽  
Electronic Band ◽  
Structure Calculations ◽  
Centrosymmetric Structure

Structural optimization, magnetic ground state and electronic structure calculations of tetragonal PbMnO3have been carried out using local density approximation (LDA) implementations of density functional theory (DFT). Structural optimizations were done on tetragonal P4mm (non-centrosymmetric) and P4/mmm (centrosymmetric) structures using experimental lattice parameters and our results indicate that P4mm is more stable than P4/mmm. In order to determine the stable magnetic ground state of PbMnO3, total energies for different magnetic configurations such as nonmagnetic (NM), ferromagnetic (FM) and antiferromagnetic (AFM) were computed for both P4mm and P4/mmm structures. The total energy results reveal that the FM non-centrosymmetric structure is found to be the most stable magnetic ground state. The electronic band structure, density of states (DOS) and the electron localization function (ELF) were calculated for the stable FM structure. ELF revealed the distorted non-centrosymmetric structure. The band structure and DOS for the majority spins of FM PbMnO3showed no band gap at the Fermi level. However, a gap opens up at the Fermi level in minority spin channel suggesting that it could be a half-metal and a potential spintronic candidate.

scholarly journals Ground-State Electronic Structure of Vanadium(III) Trisoxalate in Hydrated Compounds

2009 ◽  
Vol 48 (16) ◽  
pp. 7750-7764 ◽  
Author(s):  
Kevin R. Kittilstved ◽  
Lilit Aboshyan Sorgho ◽  
Nahid Amstutz ◽  
Philip L.W. Tregenna-Piggott ◽  
Andreas Hauser
Keyword(s):  
Electronic Structure ◽  
Ground State
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