| Abstract
| - The computation of indirect nuclear spin−spin coupling constants, based on the relativistic two-component zeroth order regular approximate Hamiltonian, has been recently implemented by us into theAmsterdam Density Functional program. Applications of the code for the calculation of one-bond metal−ligand couplings of coordinatively unsaturated compounds containing 195Pt and 199Hg, including spin−orbitcoupling or coordination effects by solvent molecules, show that relativistic density functional calculationsare able to reproduce the experimental findings with good accuracy for the systems under investigation. Spin−orbit effects are rather small for these cases, while coordination of the heavy atoms by solvent molecules hasa great impact on the calculated couplings. Experimental trends for different solvents are reproduced. Anorbital-based analysis of the solvent effect is presented. The scalar relativistic increase of the coupling constantsis of the same order of magnitude as the nonrelativistically obtained values, making a relativistic treatmentessential for obtaining quantitatively correct results. Solvent effects can be of similar importance.
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