Exact Two-Component Theory Becoming an Efficient Tool for NMR Shieldings and Shifts with Spin-Orbit Coupling DOI Creative Commons
Yannick J. Franzke, Christof Holzer

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

Exact Two-Component Theory Becoming an Efficient Tool for NMR Shieldings and Shifts with Spin-Orbit Coupling DOI Creative Commons
Yannick J. Franzke, Christof Holzer

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

Citations

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