Validation of relativistic DFT approaches to the calculation of NMR chemical shifts in square-planar Pt2+ and Au3+ complexes

PAWLAK, Tomasz, Markéta MUNZAROVÁ, Leszek PAZDERSKI and Radek MAREK. Validation of relativistic DFT approaches to the calculation of NMR chemical shifts in square-planar Pt2+ and Au3+ complexes. Journal of Chemical Theory and Computation. ACS, 2011, vol. 7, No 12, p. 3909-3923. ISSN 1549-9618. Available from: https://dx.doi.org/10.1021/ct200366n.

Basic information

• Original name: Validation of relativistic DFT approaches to the calculation of NMR chemical shifts in square-planar Pt2+ and Au3+ complexes
• Authors: PAWLAK, Tomasz (616 Poland, belonging to the institution), Markéta MUNZAROVÁ (203 Czech Republic, belonging to the institution), Leszek PAZDERSKI (616 Poland) and Radek MAREK (203 Czech Republic, guarantor, belonging to the institution).
• Edition: Journal of Chemical Theory and Computation, ACS, 2011, 1549-9618.

Other information

• Original language: English
• Type of outcome: Article in a journal
• Field of Study: 10403 Physical chemistry
• Country of publisher: United States of America
• Confidentiality degree: is not subject to a state or trade secret
• WWW: DOI: 10.1021/ct200366n
• Impact factor: Impact factor: 5.215
• RIV identification code: RIV/00216224:14740/11:00053848
• Organization unit: Central European Institute of Technology
• Doi: http://dx.doi.org/10.1021/ct200366n
• UT WoS: 000298118000007
• Keywords in English: Nuclear magnetic shielding; transition metal; density-functional theory; spin-orbit coupling; solvent effect; relativistic effect; exact-exchange admixture
• Tags: ok, rivok
• Tags: International impact, Reviewed

Abstract

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.

Links

• ED1.1.00/02.0068, research and development project: Name: CEITEC - central european institute of technology
• LC06030, research and development project: Name: Biomolekulární centrum

Investor: Ministry of Education, Youth and Sports of the CR, Biomolecular centre

• MSM0021622413, plan (intention): Name: Proteiny v metabolismu a při interakci organismů s prostředím

Investor: Ministry of Education, Youth and Sports of the CR, Proteins in metabolism and interaction of organisms with the environment