Electronic g-tensors of solvated molecules using the polarizable continuum model.
We present the implementation of density functional response theory combined with the polarizable continuum model (PCM), enabling first principles calculations of molecular g-tensors of solvated molecules. The calculated g-tensor shifts are compared with experimental g-tensor shifts obtained from electron paramagnetic resonance spectra for a few solvated species. The results indicate qualitative agreement between the calculations and the experimental data for aprotic solvents, whereas PCM fails to reproduce the electronic g-tensor behavior for protic solvents. This failure of PCM for protic solvents can be resolved by including into the model those solvent molecules which are involved in hydrogen bonding with the solute. The results for the protic solvents show that the explicit inclusion of the solvent molecules of the first solvation sphere is not sufficient in order to reproduce the behavior of the electronic g-tensor in protic solvents, and that better agreement with experimental data can be obtained by including the long-range electrostatic effects accounted for by the PCM approach on top of the explicit hydrogen-bonded complexes.
Rinkevicius
Zilvinas
Z
Laboratory of Theoretical Chemistry, The Royal Institute of Technology, SCFAB, SE-10691 Stockholm, Sweden.
Telyatnyk
Lyudmyla
L
Vahtras
Olav
O
Ruud
Kenneth
K