145 research outputs found
Fast Ionic Conductivity in the Most Lithium-Rich Phosphidosilicate Li14SiP6.
Solid electrolytes with superionic conductivity are required as a main component for all-solid-state batteries. Here we present a novel solid electrolyte with three-dimensional conducting pathways based on "lithium-rich" phosphidosilicates with ionic conductivity of σ > 10-3 S cm-1 at room temperature and activation energy of 30-32 kJ mol-1 expanding the recently introduced family of lithium phosphidotetrelates. Aiming toward higher lithium ion conductivities, systematic investigations of lithium phosphidosilicates gave access to the so far lithium-richest compound within this class of materials. The crystalline material (space group Fm3m), which shows reversible thermal phase transitions, can be readily obtained by ball mill synthesis from the elements followed by moderate thermal treatment of the mixture. Lithium diffusion pathways via both tetrahedral and octahedral voids are analyzed by temperature-dependent powder neutron diffraction measurements in combination with maximum entropy method and DFT calculations. Moreover, the lithium ion mobility structurally indicated by a disordered Li/Si occupancy in the tetrahedral voids plus partially filled octahedral voids is studied by temperature-dependent impedance and 7Li NMR spectroscopy
Sequential decoupling of negative-energy states in Douglas-Kroll-Hess theory
Here, we review the historical development, current status, and prospects of
Douglas--Kroll--Hess theory as a quantum chemical relativistic electrons-only
theory.Comment: 15 page
Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins
Bioinorganic canon states that active-site
thiolate coordination promotes rapid electron transfer (ET)
to and from type 1 copper proteins. In recent work, we have
found that copper ET sites in proteins also can be constructed
without thiolate ligation (called “type zero” sites). Here we
report multifrequency electron paramagnetic resonance
(EPR), magnetic circular dichroism (MCD), and nuclear
magnetic resonance (NMR) spectroscopic data together with
density functional theory (DFT) and spectroscopy-oriented
configuration interaction (SORCI) calculations for type zero Pseudomonas aeruginosa azurin variants. Wild-type (type 1) and type
zero copper centers experience virtually identical ligand fields. Moreover, O-donor covalency is enhanced in type zero centers
relative that in the C112D (type 2) protein. At the same time, N-donor covalency is reduced in a similar fashion to type 1
centers. QM/MM and SORCI calculations show that the electronic structures of type zero and type 2 are intimately linked to the
orientation and coordination mode of the carboxylate ligand, which in turn is influenced by outer-sphere hydrogen bonding
Structural Similarity on Multiple Length Scales and Its Relation to Devitrification Mechanism: A Solid-State NMR Study of Alkali Diborate Glasses and Crystals
New Strategies in Modeling Electronic Structures and Properties with Applications to Actinides
This chapter discusses contemporary quantum chemical methods and provides
general insights into modern electronic structure theory with a focus on
heavy-element-containing compounds. We first give a short overview of
relativistic Hamiltonians that are frequently applied to account for
relativistic effects. Then, we scrutinize various quantum chemistry methods
that approximate the -electron wave function. In this respect, we will
review the most popular single- and multi-reference approaches that have been
developed to model the multi-reference nature of heavy element compounds and
their ground- and excited-state electronic structures. Specifically, we
introduce various flavors of post-Hartree--Fock methods and optimization
schemes like the complete active space self-consistent field method, the
configuration interaction approach, the Fock-space coupled cluster model, the
pair-coupled cluster doubles ansatz, also known as the antisymmetric product of
1 reference orbital geminal, and the density matrix renormalization group
algorithm. Furthermore, we will illustrate how concepts of quantum information
theory provide us with a qualitative understanding of complex electronic
structures using the picture of interacting orbitals. While modern quantum
chemistry facilitates a quantitative description of atoms and molecules as well
as their properties, concepts of quantum information theory offer new
strategies for a qualitative interpretation that can shed new light onto the
chemistry of complex molecular compounds.Comment: 43 pages, 3 figures, Version of Recor
Intermediate-Range Order of Alkali Disilicate Glasses and Its Relation to the Devitrification Mechanism
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