A5079304905- Advanced NMR Techniques and Applications
- Magnetism in coordination complexes
- Advanced Chemical Physics Studies
- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Electron Spin Resonance Studies
- Synthesis and characterization of novel inorganic/organometallic compounds
- Organometallic Complex Synthesis and Catalysis
- Inorganic Chemistry and Materials
- Molecular spectroscopy and chirality
- Nanocluster Synthesis and Applications
- Synthesis and Properties of Aromatic Compounds
- Spectroscopy and Quantum Chemical Studies
- Synthesis and Reactivity of Heterocycles
- Advanced Condensed Matter Physics
- Crystallography and molecular interactions
- Inorganic Fluorides and Related Compounds
- Porphyrin and Phthalocyanine Chemistry
- Physics of Superconductivity and Magnetism
- Nuclear physics research studies
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Supramolecular Self-Assembly in Materials
- Catalysis and Oxidation Reactions
- Photochemistry and Electron Transfer Studies
- High-pressure geophysics and materials
Karlsruhe Institute of Technology
2015-2025
Schott (Germany)
2023-2025
Friedrich Schiller University Jena
2023-2025
Institute of Materials Research of the Slovak Academy of Sciences
2025
Institute of Nanotechnology
2025
Philipps University of Marburg
2020-2024
University of Siegen
2023
Karlsruhe University of Education
2019
University of Helsinki
2017
TURBOMOLE is a collaborative, multi-national software development project aiming to provide highly efficient and stable computational tools for quantum chemical simulations of molecules, clusters, periodic systems, solutions. The suite optimized widely available, inexpensive, resource-efficient hardware such as multi-core workstations small computer clusters. specializes in electronic structure methods with outstanding accuracy-cost ratio, density functional theory including local hybrids...
We present property-tailored all-electron relativistic Karlsruhe basis sets for the elements hydrogen to radon. The modifications described herein use at most four additional primitive functions and re-optimized contraction coefficients of inner-most segment. Thus, shielding constants are improved while maintaining compactness set. A large set 255 closed-shell molecules was used assess quality developed bases throughout periodic table elements.
We present an efficient algorithm for one- and two-component analytical energy gradients with respect to nuclear displacements in the exact decoupling approach one-electron Dirac equation (X2C). Our is a generalization of spin-free ansatz by Cheng Gauss [J. Chem. Phys. 135, 084114 (2011)], where perturbed Hamiltonian calculated solving first-order response equation. Computational costs are drastically reduced applying diagonal local approximation unitary transformation (DLU) [D. Peng M....
A comprehensive overview of the performance local hybrid functionals for molecular properties like excited states, ionization potentials within GW framework, polarizabilities, magnetizabilities, NMR chemical shifts, and spin–spin coupling constants is presented. We apply generalization kinetic energy, τ, with paramagnetic current density to all magnetic excitation energies from time-dependent functional theory. This restores gauge invariance these properties. Different ansätze mixing...
An efficient formulation of scalar-relativistic NMR shielding tensors based on (one-electron) spin-free exact two-component theory (X2C) is presented. It utilizes the diagonal local approximation to unitary decoupling matrix (DLU), which we recently applied analytical derivatives [ J. Chem. Phys. 2018, 148, 104110]. This allows for routine calculations large molecules with heavy atoms. Here, computation times all nuclei formally scale cubically size system, while memory demands increase...
A damped-response formalism in the GW approximation to Bethe–Salpeter equation (BSE) is presented and implemented. It based on a quasirelativistic two-component (2c) approach that includes scalar-relativistic spin–orbit effects derived from one-electron Dirac equation. generalised solver, which also allows calculate static, dynamic polarisabilites, discussed detail. Throughout our implementation, resolution-of-the-identity employed reduce computational effort. The performance of 2c GW-BSE...
Local hybrid functionals are a more flexible class of density functional approximations, allowing for position-dependent admixture exact exchange. This additional flexibility, however, comes with involved mathematical form and complicated design. A common denominator previously constructed local is the usage thermochemical benchmark data to construct these functionals. Herein, we design without relying on data. Instead, it in ab initio manner, following principles modern meta-generalized...
The occurrence of aromaticity in organic molecules is widely accepted, but its purely metallic systems less widespread. Molecules comprising only metal atoms (M) are known to be able exhibit aromatic behaviour, sustaining ring currents inside an external magnetic field along M-M connection axes (σ-aromaticity) or above and below the plane (π-aromaticity) for cyclic cage-type compounds. However, all-metal compounds provide extension electrons' mobility also other directions. Here, we show...
Meta-generalized gradient approximations (meta-GGAs) and local hybrid functionals generally depend on the kinetic energy density τ. For magnetic properties, this necessitates generalizations to ensure gauge invariance. In most implementations, τ is generalized by incorporating external field. However, introduces artifacts in response of matrix does not satisfy iso-orbital constraint. Here, we extend previous approaches based current paramagnetic nuclear resonance (NMR) shieldings electron...
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...
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,...
Segmented contracted basis sets of quadruple-ζ quality for exact two-component (X2C) calculations are presented the elements H-Rn. These all-electron relativistic counterparts Karlsruhe "def2" and "dhf" systems bases, which were designed Hartree-Fock density functional treatments and-with a somewhat extended set-also correlated treatments. The bases optimized with analytical set gradients finite nucleus model based on Gaussian charge distribution at scalar-relativistic X2C level. Extensions...
A quasi-relativistic implementation of NMR indirect spin–spin coupling constants is presented. The exact two-component (X2C) Hamiltonian and its diagonal local approximation to the unitary decoupling transformation (DLU) are utilized together with (modified) screened nuclear spin–orbit approach. In a restricted kinetic balance, finite nucleus model available for both scalar vector potentials. supports density functionals up fourth rung Jacob's ladder, i.e., (range-separated) hybrid based on...
We present the first steps to extend Green's function GW method and Bethe-Salpeter equation (BSE) molecular response properties such as nuclear magnetic resonance (NMR) indirect spin-spin coupling constants. discuss both a nonrelativistic one-component quasi-relativistic two-component formalism. The latter describes scalar-relativistic spin-orbit effects allows us study heavy-element systems with reasonable accuracy. Efficiency is maintained by application of resolution identity...
We present an exact two-component (X2C) ansatz for the EPR g tensor using gauge-including atomic orbitals (GIAOs) and a magnetically balanced basis set expansion. In contrast to previous X2C four-component relativistic ansätze tensor, this implementation results in gauge-origin-invariant formalism. Furthermore, derivatives of decoupling matrix are incorporated form complete analytical derivative Hamiltonian. To reduce associated computational costs, we apply diagonal local approximation...
Relativistic two-component density functional calculations are carried out in a non-collinear formalism to describe spin-orbit interactions, where the exchange-correlation is constructed as generalization of non-relativistic approximation. Contrary theory (DFT), coupling, however, leads non-vanishing paramagnetic current density. Density functionals depending on kinetic energy density, such meta-generalized gradient approximations, should therefore be framework DFT (CDFT). The latter has...
The temperature-dependent Fermi-contact and pseudocontact terms are important contributions to the paramagnetic NMR shielding tensor. Herein, we augment scalar-relativistic (local) exact two-component (X2C) framework with spin-orbit perturbation theory including screened nuclear correction for EPR hyperfine coupling g tensor compute these terms. accuracy of this perturbative ansatz is assessed self-consistent four-component treatments serving as reference. This shows that interaction...
The self-consistent and complex spin-orbit exact two-component (X2C) formalism for NMR spin-spin coupling constants [ J. Chem. Theory Comput. 17, 2021, 3874-3994] is reduced to a scalar one-component ansatz. This way, the first-order response term can be partitioned into Fermi-contact (FC) spin-dipole (SD) interactions as well paramagnetic (PSO) contribution. FC+SD terms are real symmetric, while PSO purely imaginary antisymmetric. relativistic approach combined with modern density...
We present a gauge-origin invariant exact two-component (X2C) approach within modern density functional framework, supporting meta-generalized gradient approximations such as TPSS and range-separated hybrid functionals CAM-B3LYP. The complete exchange-correlation kernel is applied, including the direct contribution of field-dependent basis functions reorthonormalization from perturbed overlap matrix. Additionally, finite nucleus model available for electron-nucleus potential vector...
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...
Herein, the synthesis of new low-valent Group 14 phosphinidenide complexes [({SIDipp}P)2 M] exhibiting P-M pπ-pπ interactions (SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene, M=Ge, Sn, Pb), is presented. These compounds were investigated by means structural, spectroscopic, and quantum-chemical methods. Furthermore, monosubstituted [(SIDippP)MX]2 (M=Sn, X=Cl; M=Pb, X=Br) are presented, which show dimeric structures instead multiple bonding interaction.
We present an efficient implementation of paramagnetic NMR shielding tensors and shifts in a nonrelativistic scalar-relativistic density functional theory framework. For the latter, we make use scalar exact two-component Hamiltonian its local approximation, generally apply well established (multipole-accelerated) resolution identity approximation seminumerical exchange approximation. The perturbed matrix calculation is further used to study magnetically induced current ring currents...
We present a highly efficient implementation of the electron-nucleus hyperfine coupling matrix within one-electron exact two-component (X2C) theory. The complete derivative X2C Hamiltonian is formed, that is, derivatives unitary decoupling transformation are considered. This requires solution response and Sylvester equations, consequently increasing computational costs. Therefore, we apply diagonal local approximation to (DLU). finite nucleus model employed for both scalar potential vector...