TURBOMOLE: Today and Tomorrow

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

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Reducing Exact Two-Component Theory for NMR Couplings to a One-Component Approach: Efficiency and Accuracy

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

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Exact two-component theory becoming an efficient tool for NMR shieldings and shifts with spin–orbit coupling

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

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Polydentate Amidinato‐Silylenes, ‐Germylenes and ‐Stannylenes

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(33)

Published: April 12, 2024

This review article focuses on amidinatotetrylenes that potentially can (or have already shown to) behave as bi- or tridentate ligands because they contain at least one amidinatotetrylene moiety (silylene, germylene stannylene) and more) additional coordinable fragment(s). Currently, are being widely used in coordination chemistry, small molecule activation catalysis. classifies those been isolated transition metal-free compounds into five families differ the position(s) of donor group(s) (D) moiety, namely: ED{R

Language: Английский

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A General and Transferable Local Hybrid Functional for Electronic Structure Theory and Many-Fermion Approaches

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

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Exact Two-Component Theory Becoming an Efficient Tool for NMR Shieldings and Shifts with Spin-Orbit Coupling

Published: Aug. 25, 2023

We present a gauge-origin invariant exact two-component (X2C) approach within modern density functional framework, supporting meta-generalized gradient approximations (meta-GGAs) 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 (DLU) 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 NMR shifts ligand with about 2400 requires less than one hour functionals. Further, impact spin-orbit coupling on nucleus-independent chemical corresponding ring currents all-metal aromatic systems studied.

Language: Английский

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Heteroleptic Anionic Cobalt(II) Pivalate Complex with a Bridging Trimethylsiloxy Ligand: Synthesis, Structure, and Formation Mechanism

Russian Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 68(9), P. 1228 - 1236

Published: Sept. 1, 2023

Language: Английский

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Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(6), P. 3118 - 3128

Published: Jan. 30, 2024

E(hmds)(bqfam) (E = Ge (1a), Sn (1b); hmds N(SiMe3)2, bqfam N,N′-bis(quinol-8-yl)formamidinate), which are amidinatotetrylenes equipped with quinol-8-yl fragments on the amidinate N atoms, have been synthesized from formamidine Hbqfam and Ge(hmds)2 or SnCl(hmds). Both 1a 1b fluxional in solution at room temperature, as E atom oscillates being attached to two atoms chelated by an its closest quinolyl (both situations similarly stable according density functional theory calculations). The group of is still reactive deprotonation another equivalent can be achieved, allowing formation homoleptic derivatives E(bqfam)2 Ge, Sn). reactions [AuCl(tht)] (tht tetrahydrothiophene), [PdCl2(MeCN)2], [PtCl2(cod)] (cod cycloocta-1,5-diene), [Ru3(CO)12] [Co2(CO)8] investigated. gold(I) complexes [AuCl{κE-E(hmds)(bqfam)}] Sn) a monodentate κE-tetrylene ligand display behavior same that 1b. However, palladium(II) platinum(II) [MCl{κ3E,N,N′-ECl(hmds)(bqfam)}] (M Pd, Pt; contain κ3E,N,N′-chloridotetryl arises insertion tetrylene into M–Cl bond coordination metal center. Finally, binuclear ruthenium(0) cobalt(0) [Ru2{μE-κ3E,N,N′-E(hmds)(bqfam)}(CO)6] [Co2{μE-κ3E,N,N′-E(hmds)(bqfam)}(μ-CO)(CO)4] related κ3E,N,N′-tetrylene bridges through atom. For κ3E,N,N′-metal complexes, fragment not pendant all germanium compounds but, for tin derivatives, (in Pd Pt complexes) may interact Ru2 Co2

Language: Английский

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Exact Two-Component Theory Becoming an Efficient Tool for NMR Shieldings and Shifts with Spin-Orbit Coupling

Published: Aug. 8, 2023

We present a gauge-origin invariant exact two-component (X2C) approach within modern density functional framework, supporting meta-generalized gradient approximations (meta-GGAs) 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 transformation (DLU) 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 NMR shifts ligand with about 2400 require less than an hour functionals. Further, impact spin-orbit coupling on nucleus-independent chemical corresponding ring currents all-metal aromatic systems studied.

Language: Английский

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Exact Two-Component Theory Becoming an Efficient Tool for NMR Shieldings and Shifts with Spin-Orbit Coupling

Published: Aug. 9, 2023

We present a gauge-origin invariant exact two-component (X2C) approach within modern density functional framework, supporting meta-generalized gradient approximations (meta-GGAs) 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 (DLU) 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 NMR shifts ligand with about 2400 requires less than one hour functionals. Further, impact spin-orbit coupling on nucleus-independent chemical corresponding ring currents all-metal aromatic systems studied.

Language: Английский

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