Four-component relativistic density functional theory with the polarisable continuum model: application to EPR parameters and paramagnetic NMR shifts

被引:16
作者
Di Remigio, Roberto [1 ]
Repisky, Michal [1 ]
Komorovsky, Stanislav [1 ]
Hrobarik, Peter [2 ]
Frediani, Luca [1 ]
Ruud, Kenneth [1 ]
机构
[1] Univ Tromso, Ctr Theoret & Computat Chem, Dept Chem, Tromso, Norway
[2] Tech Univ Berlin, Inst Chem, Berlin, Germany
关键词
Relativity; Dirac-Kohn-Sham; EPR; paramagnetic; NMR; ELECTRONIC G-TENSORS; TRANSITION-METAL-COMPLEXES; SPIN COUPLING-CONSTANTS; ORDER REGULAR APPROXIMATION; MOLECULAR HYPERFINE INTERACTIONS; MATRIX RENORMALIZATION-GROUP; CHEMICAL-SHIFTS; PERTURBATIONAL TREATMENT; RESONANCE PROPERTIES; SCREENING MODEL;
D O I
10.1080/00268976.2016.1239846
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The description of chemical phenomena in solution is as challenging as it is important for the accurate calculation of molecular properties. Here, we present the implementation of the polarisable continuum model (PCM) in the four-component Dirac-Kohn-Sham density functional theory framework, offering a cost-effective way to concurrently model solvent and relativistic effects. The implementation is based on the matrix representation of theDirac-Coulomb Hamiltonian in the basis of restricted kinetically balancedGaussian-type functions, exploiting a non-collinear Kramer's unrestricted formalism implemented in the program ReSpect, and the integral equation formalism of the PCM available through the stand-alone library PCMSolver. Calculations of electron paramagnetic resonance parameters (g-tensors and hyperfine coupling A-tensors), as well as of the temperature-dependent contribution to paramagnetic nuclear magnetic resonance (pNMR) shifts, are presented to validate the model and to demonstrate the importance of taking both relativistic and solvent effects into account for magnetic properties. As shown for selected Ru and Os complexes, the solvent shiftsmay amount to as much as 25% of the gas-phase values for g-tensor components and even more for pNMR shifts in some extreme cases. [GRAPHICS]
引用
收藏
页码:214 / 227
页数:14
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