| Autor: |
Olejniczak, Malgorzata, Bast, Radovan, Gomes, Andre Severo Pereira |
| Rok vydání: |
2016 |
| Předmět: |
|
| Druh dokumentu: |
Working Paper |
| DOI: |
10.1039/C6CP08561J |
| Popis: |
We report an implementation of the nuclear magnetic resonance (NMR) shielding ($\sigma$), isotope-independent indirect spin-spin coupling ($K$) and the magnetizability ($\xi$) tensors in the frozen density embedding (FDE) scheme using the four-component (4c) relativistic Dirac--Coulomb (DC) Hamiltonian and the non-collinear spin density functional theory (SDFT). The formalism takes into account the magnetic balance between the large and the small components of molecular spinors and assures the gauge-origin independence of NMR shielding and magnetizability results. This implementation has been applied to hydrogen-bonded HXH$\cdots$OH$_2$ complexes (X = Se, Te, Po) and compared with the supermolecular calculations and with the approach based on the integration of the magnetically induced current density vector. A comparison with the approximate Zeroth-Order Regular Approximation (ZORA) Hamiltonian indicates non-negligible differences in $\sigma$ and $K$ in the HPoH$\cdots$OH$_2$ complex, and calls for a thourough comparison of ZORA and DC in the description of environment effects on NMR parameters for molecular systems with heavy elements. |
| Databáze: |
arXiv |
| Externí odkaz: |
|
