Themed collection Quantum Theory: The Challenge of Transition Metal Complexes
Quantum Theory: The Challenge of Transition Metal Complexes
Chantal Daniel, Leticia González and Frank Neese introduce the Physical Chemistry Chemical Physics themed collection on Quantum Theory: The Challenge of Transition Metal Complexes.
Behind the scenes of spin-forbidden decay pathways in transition metal complexes
Understanding the microscopic origin of spin-forbidden radiative and non-radiative photophysics of transition metal complexes with reference to spin–orbit coupling.
Coupled transport of electrons and protons in a bacterial cytochrome c oxidase—DFT calculated properties compared to structures and spectroscopies
DFT calculated structures, vibrational frequencies, and energies provide insights into the reaction/proton pumping cycle of cytochrome c oxidase.
A revisit of the bond valence model makes it universal
The application of Pauling's principles to any type of chemical bond can be validated using recent quantum chemistry data (bond orders), thus making them universal.
Theoretical modeling of the singlet–triplet spin transition in different Ni(II)-diketo-pyrphyrin-based metal–ligand octahedral complexes
The structural stability, charge transfer effects and strength of the spin–orbit couplings in different Ni(II)–ligand complexes have been studied at the DFT (B3LYP and CAM-B3LYP) and coupled cluster (DLPNO-CCSD(T)) levels of theory.
Accurate and rapid prediction of pKa of transition metal complexes: semiempirical quantum chemistry with a data-augmented approach
Data-augmented high-throughput QM approach to compute pKa of transition metal hydride complexes with hDFT accuracy and low cost.
Re-examining the electronic structure of fluorescent tetra-silver clusters in zeolites
Zeolite encapsulated complexes of silver clusters show luminescence properties that are tuneable by varying the ligand.
Theoretical study on conformational energies of transition metal complexes
Conformational energies are an important chemical property for which a performance assessment of theoretical methods is mandatory. Efficient low-cost methods are valuable for the generation and energetic ranking of conformers.
Spin-state energetics of metallocenes: How do best wave function and density functional theory results compare with the experimental data?
Benchmarking quantum-chemical methods against experiment-derived spin-state energetics of metallocenes.
The effect of N-heterocyclic carbene units on the absorption spectra of Fe(II) complexes: a challenge for theory
The absorption spectra of five Fe(II) homoleptic and heteroleptic complexes containing strong sigma-donating N-heterocyclic carbene (NHC) and polypyridyl ligands have been theoretically characterized using a tuned range-separation functional.
The decisive role of 4f-covalency in the structural direction and oxidation state of XPrO compounds (X: group 13 to 17 elements)
Through a theoretical study, the molecular structures of XPrO are found to be correlated with the Pr oxidation state; compounds with higher oxidation state have more important 4f involvement in the chemical bonding and thus the structure becomes more linear.
Electronic and spin structures of CaMn4Ox clusters in the S0 state of the oxygen evolving complex of photosystem II. Domain-based local pair natural orbital (DLPNO) coupled-cluster (CC) calculations using optimized geometries and natural orbitals (UNO) by hybrid density functional theory (HDFT) calculations
Domain-based local pair natural orbital coupled cluster single and double with triple perturbation correction methods were performed to elucidate the stabilities of 10 intermediate structures of the CaMn4Ox cluster of the oxygen evolving complex of photosystem II.
Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds
DFTB3+U for transition metal systems.
Quantitative calculations of the non-radiative rate of phosphorescent Ir(III) complexes
We calculated, quantitatively, the non-radiative rate of a family of Ir(III) phosphors by two methods based on transition state theory.
How external perturbations affect the chemoselectivity of substrate activation by cytochrome P450 OleTJE
Computational studies on the bifurcation pathways of the fatty acid activating cytochrome P450 enzyme OleTJE show that external perturbations of the protein affect the product distributions and reaction rates.
Palladium-catalysed methoxycarbonylation of ethene with bidentate diphosphine ligands: a density functional theory study
The mechanism and origin of selectivity of Pd-catalysed formation of methyl propionate is elucidated through DFT calculations.
Cyclic (alkyl)(amino)carbenes in organic and organometallic methane C–H activation: a DFT and MCSCF study
Density functional theory (DFT) and multi-configurational self-consistent field (MCSCF) calculations are used to investigate the electronic and steric properties of cyclic (alkyl)(amino)carbenes (CAACs).
Can one use the electronic absorption spectra of metalloporphyrins to benchmark electronic structure methods? A case study on the cobalt porphyrin
One must be skeptical about the reference chosen to benchmark electronic structure calculations, such as DFT functionals and active spaces for multireference calculations.
Understanding the luminescence properties of Cu(I) complexes: a quantum chemical perusal
Electronic structures and excited-state properties of Cu(I) complexes with varying coordination numbers have been investigated by means of advanced quantum chemical methods.
QM/MM MD simulations reveal an asynchronous PCET mechanism for nitrite reduction by copper nitrite reductase
The nitrite reduction in copper nitrite reductase is found to proceed through an asynchronous proton-coupled electron transfer (PCET) mechanism, with electron transfer from T1-Cu to T2-Cu preceding the proton transfer from Asp98 to nitrite.
Optical absorption properties of metal–organic frameworks: solid state versus molecular perspective
The challenges of the description of excited states in MOF crystals are addressed by periodic and molecular computations.
Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics
The origin of distinct 3d vs. 4d transition metal complex sensitivity to exchange is explored over a large data set.
An ab initio multireference study of reductive eliminations from organoferrates(III) in the gas-phase: it is all about the spin state
The reductive elimination reaction from organoferrates(III) of the composition [FeR3R′]− is studied by state-of-the-art multireference electronic structure calculations.
Quantum chemical topology and natural bond orbital analysis of M–O covalency in M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np)
V XC(M,O): the exchange–correlation metric quantifies covalency between M and O atomic basins in M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np).
Spin-symmetrised structures and vibrational frequencies of iron–sulfur clusters
The recently developed Extended Broken Symmetry technique is employed for studying a bi- and tetra-nuclear iron–sulfur cluster with respect to magnetic, structural and, most importantly, vibrational properties.
Relativity or aromaticity? A first-principles perspective of chemical shifts in osmabenzene and osmapentalene derivatives
The topology of the magnetically induced current density in osmabenzene suggests that the molecule is a novel type of Craig–Möbius aromatic system.
Simulations of valence excited states in coordination complexes reached through hard X-ray scattering
Theoretical guide to the valence electronic structure information that can be extracted from hard X-ray scattering experiments.
About this collection
This collection aims at promoting the power of quantum theory at deciphering electronic structure, bonding, nuclear relaxation, (photo-) chemical reactivity, catalytic and enzymatic activities of transition metal complexes. The scope of this themed collection is to stimulate the dissemination of state-of-the-art methods and to demonstrate their potential in the interpretation and prediction of a variety of fascinating spectroscopic, optical and magnetic properties in transition metal complexes. By exploring the intimacy of matter, particularly complex in coordination chemistry, quantum theory does not only provide accurate structural understanding but also in-depth knowledge of the processes that control primary functions, either at the molecular scale or in specific environments.