Experimental Evidence of a Diatropic Ring Current Occurring in the Metal Cluster [{(C5Me4H)2La}3Sn2Bi3]2– DOI Creative Commons
Stefanie Dehnen, Yannick R. Lohse,

Julia Rienmueller

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: Oct. 16, 2023

Abstract Aromaticity, in its most widely known form, describes the phenomenon of cyclic delocalization (4n+2)π-electrons a planar molecule, which leads to energetic stabilization and is accompanied by ring current flowing within molecular plane upon exposing molecule magnetic field.1–4 This concept, has been for organic molecules century, only recently discussed purely metallic compounds. On basis quantum chemical calculations, σ-, π-, also ϕ-aromatic compounds were identified.5–9 However, due either such compounds’ insolubility or lack suitable NMR handles, this not yet experimentally proven date. Here we close gap providing first experimental evidence current. Quantum calculations on novel Zintl cluster [{(C5Me4H)2La}3Sn2Bi3] 2− reveal diatropic current, indicative an aromatic behavior, caused interaction inner (Sn2Bi3)5– unit with three [(C5Me4H)2La]+ complex fragments. It {Ln3Bi3} very uncommon species, ternary exhibiting f-block metal fragments surface. Different from all studies so far, was proved means solid-state MAS spectroscopy. In excellent agreement prediction, 1 H shifts protons at (C5Me4H)− ligands that are closest core shifted low field. finding long sought rationalizes numerous hypotheses made related clusters.

Language: Английский

Application of the noncollinear Scalmani–Frisch formalism to current density functional theory DOI Creative Commons
Yannick J. Franzke, Ansgar Pausch, Christof Holzer

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(8)

Published: Feb. 25, 2025

We generalize the noncollinear formalism proposed by Scalmani and Frisch [J. Chem. Theory Comput. 8, 2193 (2012)] to include particle spin current densities for meta-generalized gradient approximations local hybrid functionals. This allows us fully impact of spin–orbit coupling in relativistic calculations applications finite magnetic fields. For latter, we use London atomic orbitals ensure gauge origin invariance. It is shown that this superior more common canonical approach calculations, as it naturally includes all three closed-shell limit avoids projection onto magnetization vector. important easily restore rotational invariance limit. In addition, Scalmani–Frisch can be made numerically stable may lead a nonvanishing torque. However, both formalisms are rotationally invariant open-shell systems

Language: Английский

Citations

2
Paramagnetic Nuclear Magnetic Resonance Shifts for Triplet Systems and Beyond with Modern Relativistic Density Functional Methods DOI
Yannick J. Franzke, Florian Bruder, Sebastian Gillhuber

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(3), P. 670 - 686

Published: Jan. 9, 2024

An efficient framework for the calculation of paramagnetic NMR (pNMR) shifts within exact two-component (X2C) theory and (current-dependent) density functional (DFT) up to class local hybrid functionals (LHFs) is presented. Generally, pNMR systems with more than one unpaired electron depend on orbital shielding contribution a temperature-dependent term. The latter includes zero-field splitting (ZFS), hyperfine coupling (HFC), g-tensor. For consistency, we calculate these three tensors at same level theory, i.e., using scalar-relativistic X2C augmented spin–orbit perturbation theory. Results chemical transition-metal complexes reveal that this X2C–DFT can yield good results both individual tensor contributions metallocenes related systems, especially if HFC constant large. small constants, relative error often large, sometimes sign may be off. 4d 5d complicated structures demonstrate limitations fully DFT-based approach. Additionally, Co-based complex very large ZFS pronounced multireference character not well described. Here, DFT-multireference necessary accurate results. Our show sufficient describe relativistic effects computationally cheaper Thus, it allows use basis sets converged HFCs. Overall, current-dependent meta-generalized gradient approximations LHFs some potential; however, currently available leave lot desired, predictive power limited.

Language: Английский

Citations

9
Beyond Electrons: Correlation and Self‐Energy in Multicomponent Density Functional Theory DOI Creative Commons
Christof Holzer, Yannick J. Franzke

ChemPhysChem, Journal Year: 2024, Volume and Issue: 25(13)

Published: March 8, 2024

Abstract Post‐Kohn‐Sham methods are used to evaluate the ground‐state correlation energy and orbital self‐energy of systems consisting multiple flavors different fermions. Starting from multicomponent density functional theory, suitable ways arrive at corresponding random‐phase approximation Green's function approximation, including relativistic effects, outlined. Given importance both this in development modern Kohn–Sham approximations, work will provide a foundation design advanced approximations. Additionally, quasiparticle energies needed study light‐matter interactions with Bethe‐Salpeter equation.

Language: Английский

Citations

7
Core-electron contributions to the magnetic response of molecules with heavy elements and their significance in aromaticity assessments DOI Creative Commons
Mesías Orozco‐Ic, Luis Soriano‐Agueda, Dage Sundholm

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(32), P. 12906 - 12921

Published: Jan. 1, 2024

This study delves into the magnetic response of core electrons and their influence on global planar three-dimensional systems containing heavy elements, employing removing valence electron (RVE) approximation.

Language: Английский

Citations

7
Relativistic Fully Self-Consistent GW for Molecules: Total Energies and Ionization Potentials DOI
Vibin Abraham, Gaurav Harsha, Dominika Zgid

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(11), P. 4579 - 4590

Published: May 23, 2024

The fully self-consistent GW (scGW) method with an iterative solution of the Dyson equation provides a consistent approach for describing ground and excited states without any dependence on mean-field reference. In this work, we present relativistic version scGW molecules containing heavy elements using exact two-component (X2C) Coulomb approximation. We benchmark SOC-81 data set closed shell first ionization potential as well one-shot GW. superior results compared to G0W0 PBE reference comparable PBE0 while also removing starting point dependence. photoelectron spectra obtained at X2C level demonstrate very good agreement experimental spectra. observe that estimation inner d-shell orbitals. Additionally, well-conserved total energy, investigate equilibrium bond length harmonic frequencies few halogen dimers scGW. Overall, our findings applicability accurate potential, spectra, energies in finite systems reasonable computational scaling.

Language: Английский

Citations

6
Zero-field splitting parameters within exact two-component theory and modern density functional theory using seminumerical integration DOI Open Access
Florian Bruder, Yannick J. Franzke, Christof Holzer

et al.

The Journal of Chemical Physics, Journal Year: 2023, Volume and Issue: 159(19)

Published: Nov. 21, 2023

An efficient implementation of zero-field splitting parameters based on the work Schmitt et al. [J. Chem. Phys. 134, 194113 (2011)] is presented. Seminumerical integration techniques are used for two-electron spin-dipole contribution and response equations spin-orbit perturbation. The original formulation further generalized. First, it extended to meta-generalized gradient approximations local hybrid functionals. For these functional classes, paramagnetic current density considered in coupled-perturbed Kohn-Sham perturbation term. Second, formulated within relativistic exact two-component theory screened nuclear (SNSO) approximation. accuracy demonstrated transition-metal diatomic main-group compounds. efficiency assessed Mn Mo complexes. Here, found that coarse grids seminumerical schemes lead drastic speedups while introducing clearly negligible errors. In addition, SNSO approximation substantially reduces computational demands leads very similar results as mean field Ansatz.

Language: Английский

Citations

10
A General and Transferable Local Hybrid Functional for Electronic Structure Theory and Many-Fermion Approaches DOI
Christof Holzer, Yannick J. Franzke

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

Density functional theory has become the workhorse of quantum physics, chemistry, and materials science. Within these fields, a broad range applications needs to be covered. These from solids molecular systems, organic inorganic or even electrons other Fermions, such as protons muons. This is emphasized by plethora density approximations that have been developed for various cases. In this work, two new local hybrid exchange-correlation functionals are constructed first-principles, promoting generality transferability. We show constraint satisfaction can achieved admixtures with full exact exchange, without sacrificing accuracy. The performance CHYF-PBE CHYF-B95 assessed thermochemical properties, excitation energies, Mössbauer isomer shifts, NMR spin-spin coupling constants, shieldings magnetizabilities, EPR hyperfine constants. Here, shows excellent throughout all tests numerically robust only requiring small grids converged results. Additionally, both easily generalized arbitrary Fermions shown electron-proton correlation energies. Therefore, we outline generated in way general purpose tools mechanical studies.

Language: Английский

Citations

3
Parallelization of Two-Electron Integrals in Spin-Free Infinite-Order Two-Component Hamiltonian DOI
Chinami Takashima, Hiromi Nakai

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

A parallelization scheme for computing two-electron integrals in a two-component relativistic theory was developed based on the spin-free infinite-order Hamiltonian. The proposed algorithm utilizes distributed data interface and memory GAMESS program. Its efficiency demonstrated by numerical assessments. Furthermore, implemented combining it with local unitary transformation, which is linear-scaling technique multiprocess calculation of total energy metal complex [Pt13(C7H7)6]2+ indicates usefulness parallel program this study.

Language: Английский

Citations

0
Benchmark Study on the Calculation of 207Pb NMR Chemical Shifts DOI Creative Commons
Thomas Gasevic, Julius B. Kleine Büning, Stefan Grimme

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(11), P. 5052 - 5064

Published: March 6, 2024

A benchmark set for the computation of 207Pb nuclear magnetic resonance (NMR) chemical shifts is presented. The PbS50 includes conformer ensembles 50 lead-containing molecular compounds and their experimentally measured NMR shifts. Various bonding motifs at Pb center with up to seven partners are included. Six different solvents were used in measurements. respective lie range between +10745 −5030 ppm. Several calculation settings assessed by evaluating computed use density functional approximations (DFAs), relativistic approaches, treatment conformational space, levels geometry optimization. Relativistic effects included explicitly zeroth order regular approximation (ZORA), which only spin–orbit variant was able yield reliable results. In total, GGAs three hybrid DFAs tested. Hybrid significantly outperform GGAs. most accurate mPW1PW a mean absolute deviation (MAD) 429 ppm PBE0 an MAD 446 Conformational influences small as rigid, but more flexible structures still benefit from Boltzmann averaging. Including explicit treatments such SO-ZORA optimization does not show any significant improvement over effective core potentials (ECPs).

Language: Английский

Citations

2
Efficient treatment of relativistic effects with periodic density functional methods: Energies, gradients, and stress tensors DOI
Yannick J. Franzke, Werner M. Schosser, Fabian Pauly

et al.

Physical review. B./Physical review. B, Journal Year: 2024, Volume and Issue: 109(16)

Published: April 23, 2024

The implementation of an efficient self-consistent field (SCF) method including both scalar-relativistic effects and spin-orbit interaction in density functional theory (DFT) is presented. We make use Gaussian-type orbitals all integrals are evaluated real space. Our supports approximations up to the level meta-generalized gradient for SCF energies gradients. latter can be used compute stress tensor consequently allow us optimize cell structure. Considering requires extension standard procedures a two-component formalism noncollinear approach open-shell systems. Here, we implemented canonical Scalmani-Frisch DFT formalisms, with hybrid range-separated functionals being presently restricted energies. demonstrate efficiency relevance electronic structure discrete systems periodic one three dimensions.

Language: Английский

Citations

2