| Autor: |
Hallmen PP; Institute of Physical Chemistry , University of Stuttgart , Pfaffenwaldring 55 , 70569 Stuttgart , Germany.; Institute of Theoretical Chemistry , University of Stuttgart , Pfaffenwaldring 55 , 70569 Stuttgart , Germany., Rauhut G; Institute of Theoretical Chemistry , University of Stuttgart , Pfaffenwaldring 55 , 70569 Stuttgart , Germany., Stoll H; Institute of Theoretical Chemistry , University of Stuttgart , Pfaffenwaldring 55 , 70569 Stuttgart , Germany., Mitrushchenkov AO; Laboratoire de Modélisation et Simulation Multi Echelle , Université Paris-Est , MSME UMR 8208, 5 bd Descartes , 77454 Marne-la-Vallée , France., van Slageren J; Institute of Physical Chemistry , University of Stuttgart , Pfaffenwaldring 55 , 70569 Stuttgart , Germany. |
| Abstrakt: |
State-averaged complete active space self-consistent field (CASSCF) calculations and a subsequent spin-orbit calculation mixing the CASSCF wave functions (CASSCF/state-interaction with spin-orbit coupling) is the conventional approach used for ab initio calculations of crystal-field splittings and magnetic properties of lanthanide complexes. However, this approach neglects dynamical correlation. Complete active space second-order perturbation theory (CASPT2) can be used to account for dynamical correlation but suffers from the well-known problems of multireference perturbation theory, e.g., intruder state problems. Variational multireference configuration interaction (MRCI) calculations do not show these problems but are usually not feasible due to the large size of real lanthanide complexes. Here, we present a quasi-local projected internally contracted MRCI approach which makes MRCI calculations of lanthanide complexes feasible and allows assessing the influence of dynamical correlation beyond second-order perturbation theory. We apply the method to two well-studied molecules, namely, [Er{N(SiMe 3 ) 2 } 3 ] and {C(NH 2 ) 3 } 5 [Er(CO 3 ) 4 ]·11H 2 O. |
