Validation of relativistic DFT approaches to the calculation of NMR chemical shifts in square-planar Pt2+ and Au3+ complexes
| Authors | |
|---|---|
| Year of publication | 2011 |
| Type | Article in Periodical |
| Magazine / Source | Journal of Chemical Theory and Computation |
| MU Faculty or unit | |
| Citation | |
| Web | DOI: 10.1021/ct200366n |
| Doi | http://dx.doi.org/10.1021/ct200366n |
| Field | Physical chemistry and theoretical chemistry |
| Keywords | Nuclear magnetic shielding; transition metal; density-functional theory; spin-orbit coupling; solvent effect; relativistic effect; exact-exchange admixture |
| Attached files | |
| Description | Recently implemented hybrid density-functional methods of calculating nuclear magnetic shielding using the two-component zeroth-order regular approximation (ZORA) approach have been employed for a series of compounds containing heavy transition-metal atoms. In this study we investigate the effects of geometry, exchange-correlation functional, solvent, and scalar-relativistic and spin-orbit corrections on the nuclear magnetic shielding - mainly for 13C and 15N atoms connected to a heavy-atom center. The 13C and 15N NMR chemical shifts are found to be best reproduced by using a B3LYP or PBE0 approach with 30 % and 40-50 % exact-exchange admixtures for the Pt2+ and Au3+ complexes, respectively. |
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