Molecular Physics, Journal Year: 2024, Volume and Issue: unknown
Published: July 1, 2024
Language: Английский
Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(20), P. 6859 - 6890
Published: June 29, 2023
TURBOMOLE is a highly optimized software suite for large-scale quantum-chemical and materials science simulations of molecules, clusters, extended systems, periodic solids. uses Gaussian basis sets has been designed with robust fast applications in mind, ranging from homogeneous heterogeneous catalysis to inorganic organic chemistry various types spectroscopy, light-matter interactions, biochemistry. This Perspective briefly surveys TURBOMOLE's functionality highlights recent developments that have taken place between 2020 2023, comprising new electronic structure methods molecules solids, previously unavailable molecular properties, embedding, dynamics approaches. Select features under development are reviewed illustrate the continuous growth program suite, including nuclear orbital methods, Hartree-Fock-based adiabatic connection models, simplified time-dependent density functional theory, relativistic effects magnetic multiscale modeling optical properties.
Language: Английский
Citations
126
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
The Journal of Chemical Physics, Journal Year: 2022, Volume and Issue: 157(3)
Published: June 27, 2022
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 (EPR) g-tensors. The impact assessed for main-group compounds transition-metal complexes considering 25 functional approximations. It shown that leads substantial improvements-especially popular Minnesota strongly constrained appropriately normed (SCAN) families. Thus, recommend use NMR EPR calculations with meta-GGAs.
Language: Английский
Citations
39
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
The Journal of Chemical Physics, Journal Year: 2022, Volume and Issue: 157(20)
Published: Nov. 7, 2022
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 previously exclusively been used regime strong magnetic fields. Herein, we present consistent CDFT approach for relativistic DFT, including coupling. Furthermore, assess importance terms ground-state energies, excitation nuclear resonance shielding, and spin-spin coupling constants, well hyperfine Δg-shifts, quadrupole interaction tensor electron (EPR) spectroscopy. most notable changes found EPR properties. impact current-dependent rises with number unpaired electrons, consequently, properties more sensitive toward CDFT. Considerable observed strongly constrained appropriately normed functionals, B97M family TASK. less important when exact exchange incorporated. At same time, kernel ensures stability response all cases. We, therefore, recommend use self-consistent calculations.
Language: Английский
Citations
37
Journal of Chemical Theory and Computation, Journal Year: 2022, Volume and Issue: 18(12), P. 7442 - 7456
Published: Nov. 23, 2022
The CASPT2+δMRCI composite approach reported in a companion paper has been extended and used to provide high-quality reference data for series of adiabatic spin gaps (defined as ΔE = Equintet - Esinglet) [FeIIL6]2+ complexes (L CNH, CO, NCH, NH3, H2O), either at nonrelativistic level or including scalar relativistic effects. These highly accurate have evaluate the performance various more approximate methods. Coupled-cluster theory with singles, doubles, perturbative triples, CCSD(T), is found agree well new Werner-type but exhibits larger underestimates by up 70 kJ/mol π-acceptor ligands, due appreciable static correlation low-spin states these systems. Widely domain-based local CCSD(T) calculations, DLPNO-CCSD(T), are shown depend very sensitively on cutoff values construct localized domains, standard not sufficient. A large number density functional approximations evaluated against data. B2PLYP double hybrid gives smallest deviations, several functionals from different rungs usual ladder hierarchy give mean absolute deviations below 20 kJ/mol. This includes B97-D semilocal functional, PBE0* global 15% exact-exchange admixture, hybrids LH07s-SVWN LH07t-SVWN. Several further achieve errors 30 (M06L-D4, SSB-D, B97-1-D4, LC-ωPBE-D4, LH12ct-SsirPW92-D4, LH12ct-SsifPW92-D4, LH14t-calPBE-D4, LHJ-HFcal-D4, hybrids) thereby also still overall outperform uncorrected CASPT2. While admixture crucial factor favoring high-spin states, present evaluations confirm that other aspects can be important well. better-performing underestimate ligands overestimate them L H2O. In contrast previous suggestion, non-self-consistent (DFT) computations top Hartree-Fock orbitals promising path produce such complexes.
Language: Английский
Citations
34
The Journal of Physical Chemistry A, Journal Year: 2022, Volume and Issue: 126(30), P. 5050 - 5069
Published: July 20, 2022
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 sufficiently described shifts; however, larger deviations found spectra principle components properties heavy elements. impact treatment further compared density functional approximation basis set. Large-scale calculations routinely possible multipole-accelerated resolution identity seminumerical exchange approximation, shown [CeTi6O3(OiPr)9(salicylate)6].
Language: Английский
Citations
31
Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(7), P. 2010 - 2028
Published: March 20, 2023
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 functional treatment up local hybrid functionals including of current density. Computational demands by factors 8-24 shown large tin compound consisting 137 atoms. Limitations ansatz critically assessed Sn, Pb, Pd, Pt compounds, i.e. not sufficient compounds featuring few heavy halogen
Language: Английский
Citations
21
Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(11), P. 3131 - 3145
Published: May 15, 2023
The applicability of reduced scaling algorithms based on auxiliary subspace methods for the correlation energy from random phase approximation (RPA) as well part self-energy obtained GW method is outlined time-reversal symmetry breaking Kohn-Sham (KS) references. updated allow an efficient evaluation RPA energies and quasiparticle molecular systems with KS references that break symmetry. latter occur, example, in magnetic fields. Furthermore, relativistic open-shell molecules also due to single determinant ansatz used. Errors reduced-scaling are shown be negligible compared reference implementations, while overall computational by 2 orders magnitude. Ionization robust even electronically complicated group trivalent lanthanoid ions. Starting energies, it subsequently light-matter interactions these can calculated using Bethe-Salpeter equation (BSE). Using combined GW-BSE method, absorption emission spectra a europium(III) complex including spin-orbit coupling.
Language: Английский
Citations
19
The Journal of Chemical Physics, Journal Year: 2023, Volume and Issue: 159(18)
Published: Nov. 8, 2023
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 throughout. Efficiency ensured by diagonal local approximation to unitary decoupling transformation in X2C well (multipole-accelerated) resolution identity Coulomb term (MARI-J, RI-J) seminumerical exchange approximation. Errors introduced these are assessed found be clearly negligible. applicability our implementation large-scale calculations demonstrated tin pincer-type system low-valent lead complexes. Here, calculation Sn nuclear magnetic resonance shifts ligand with about 2400 requires less than 1 h functionals. Further, impact spin-orbit coupling on nucleus-independent chemical corresponding ring currents all-metal aromatic systems studied.
Language: Английский
Citations
17