Beskrivelse
Despite the recent advances of four-component relativistic methods and programs, two-component relativistic methods are still widely employed due to their significantly reduced scaling. One of the two-component methods, which has been around for some time, is the zeroth order regular approximation (ZORA) [1]. In a series of studies we have investigated the performance of this approximation in the calculation of the chemical shifts of nuclear magnetic resonance (NMR) spectroscopy, the hyperfine coupling constants of electron spin resonance (ESR) spectroscopy and the electric field gradients indirectly measured in perturbed angular correlation (PAC) spectroscopy. The performance of ZORA in combination with density functional theory (DFT) is hereby judged by either the agreement with four-component calculations or experimental values.In more detail, the results of ZORA calculations of 199Hg chemical shifts [2] and the electric field gradient at Hg [3] in mercurydihalides, of the chemical shifts of the noble gases in nobel gas dimers [4], of the hyperfine coupling constants of Re and Ir in their hexafluoro complexes [5] will be compared with corresponding results of four-component calculations. Furthermore, ZORA results for the 13C chemical shifts in various Ru-carbide complexes [6] and in 3,6-dihalogen-carbazoles [7], for noble gases encapsulated in fullerenes [8] and silver complexes [9] will be compared with experimental values. Finally the basis set dependence of the ZORA results will be discussed.
[1] E. van Lenthe, E. J. Baerends, J. G. Snijders, J. Chem. Phys. 99, 4597 (1993).
[2] V. Arcisauskaite, J. I. Melo, L. Hemmingsen, S. P. A. Sauer, J. Chem. Phys. 135, 044306 (2011).
[3] V. Arcisauskaite, S. Knecht, S. P. A. Sauer, L. Hemmingsen, Phys. Chem. Chem. Phys. 14, 16070 (2012).
[4] M. Jankowska, T. Kupka, L. Stobiński, R. Faber, E. G. Lacerda Jr, S. P. A. Sauer, J. Comp. Chem. 37, 395 (2016).
[5] P. A. B. Haase, M. Repisky, J. Bendix, S. P. A. Sauer, to be published.
[6] T. J. Morsing, A. Reinholdt, S. P. A. Sauer, J. Bendix, Organometallics 35, 100 (2016).
[7] K. Radula-Janik, T. Kupka, K. Ejsmont, Z. Daszkiewicz, S. P. A. Sauer, Magn. Res. Chem. 51, 630 (2013); K. Radula-Janik, T. Kupka, K. Ejsmont, Z. Daszkiewicz, S. P. A. Sauer, Struct. Chem. 26, 997 (2015); K. Radula-Janika, T. Kupka, K. Ejsmonta, Z. Daszkiewicza, S. P. A. Sauer, Struct. Chem. 27, 199 (2016).
[8] M. Jankowska, T. Kupka, L. Stobinski, S. P. A. Sauer, to be published.
[9] S. P. A. Sauer, J. Bendix, to be published.
| Periode | 22 jul. 2016 |
|---|---|
| Begivenhedstitel | ISTCP IX 2016 Conference |
| Begivenhedstype | Konference |
| Placering | Grand Forks, ND, USAVis på kort |