Abstract Recently, some of the authors introduced the use of the Householder transformation as a simple and intuitive method for embedding local molecular fragments [see Sekaran et al., Phys. Rev. B 104, 035121 (2021) and Sekaran et al., Computation 10, 45 (2022)]. In this work, we present an…
The Institute of Chemistry is pleased to inform you that the LCQS team has recently contributed to a new article entitled “DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science” published in Phys. Chem. Chem. Phys.: https://doi.org/10.1039/D2CP02827A Con…
Abstract We report the first examples of metal-promoted double geminal activation of C(sp 3 )–H bonds of the N–CH 2 –N moiety in an imidazole-type heterocycle, leading to nickel and palladium NHC complexes under mild conditions. Reaction of the new electron-rich diphosphine 1,3-bis((di- tert…
Abstract A combined experimental/theoretical study of Ni pincer complexes with a bridgehead pyrimidine-based NHC and arylphosphino side arms revealed unique features about stepwise C–H activation, ethylene insertion into the Ni–H bond of an isolated complex followed by ethyl migration with C–CNHC…
Abstract Citronellol, one of the most used fragrance compounds worldwide, is one ingredient of Fragrance Mix II used to assess skin allergy to fragrances in dermatitis patients. Pure citronellol is non-allergenic. Main issue is it autoxidizes when exposed to air becoming then allergenic. The…
Abstract Combination of spin crossover metal ion and open-shell environment results in the mixing of high- and low- spin metal states, named as spinmerism.
Abstract Quantum embedding is a divide and conquer strategy that aims at solving the electronic Schrödinger equation of sizeable molecules or extended systems. We establish in the present work a clearer and in-principle-exact connection between density matrix embedding theory (DMET) and…
Abstract Recent progress in the field of (time-independent) ensemble density-functional theory (DFT) for excited states are reviewed. Both Gross–Oliveira–Kohn (GOK) and N-centered ensemble formalisms, which are mathematically very similar and allow for an in-principle-exact description of neutral…
Abstract Quantum embedding based on the (one-electron-reduced) density matrix is revisited by means of the unitary Householder transformation. While being exact and equivalent to (but formally simpler than) density matrix embedding theory (DMET) in the noninteracting case, the resulting…
Abstract Capturing the discontinuous shift by Δ in the exact exchange-correlation (xc) potential is the standard proposal for calculating the fundamental gap Eg from the Kohn-Sham (KS) gap ɛg within KS density functional theory (DFT) as Eg=ɛg+Δ, yet this discontinuity is absent from existing…
Summary A salt compound containing a formal Zn2+ dication only stabilized by weakly coordinated carborate anions was first structurally characterized and shown to be soluble in low polarity solvents. Based on its reactivity with alkene, alkyne and in hydrosilylation catalysis, it is a strong Lewis…
Regarding the article « Origin of ferromagnetism and magnetic anisotropy in a family of copper(II) triangles » recently published in Chemistry Eur. J., the Institute of Chemistry is pleased to inform you that the POMAM group's artwork has also been selected to feature on the cover of the last issue…
Abstract Gould and Pittalis [Phys. Rev. Lett. 123, 016401 (2019)] recently revealed a density-driven (DD) correlation energy that is specific to many-electron ensembles and must be accounted for by approximations. We derive in this Letter a general and simpler expression in terms of the ensemble…
Abstract Gross--Oliveira--Kohn (GOK) ensemble density-functional theory (GOK-DFT) is a time-\textit{independent} extension of density-functional theory (DFT) which allows to compute excited-state energies via the derivatives of the ensemble energy with respect to the ensemble weights. Contrary to…
Abstract We report a local, weight-dependent correlation density-functional approximation that incorporates information about both ground and excited states in the context of density functional theory for ensembles (eDFT). This density-functional approximation for ensembles is specially designed…
Abstract Previously reported ferromagnetic triangles (NnBu4)2[Cu3(μ‐Cl)2(μ‐4‐NO2‐pz)3Cl3] (1), (PPN)2[Cu3(μ‐Cl)2(μ‐pz)3Cl3](2), (bmim)2[Cu3(μ‐Cl)2(μ‐pz)3Cl3] (3) and newly reported (PPh4)2[Cu3(μ‐Cl)2(μ‐4‐Ph‐pz)3Cl3] (4) were studied by magnetometry, Electron Paramagnetic Resonance (EPR)…
Abstract Two (so‐called left and right) variants of N‐centered ensemble density‐functional theory (DFT) are presented. Unlike the original formulation of the theory, these variants allow for the description of systems with a fractional electron number. While conventional DFT for open systems uses…
Abstract A reformulation of site-occupation embedding theory (SOET) in terms of Green's functions is presented. Referred to as site-occupation Green's-function embedding theory (SOGET), this extension of density-functional theory for model Hamiltonians shares many features with dynamical…
Abstract Gross–Oliveira–Kohn density-functional theory (GOK-DFT) for ensembles is the DFT analog of state-averaged wavefunction-based (SA-WF) methods. In GOK-DFT, the SA (so-called ensemble) exchange-correlation (xc) energy is described by a single functional of the density which, for a fixed…
