Foreign Cooperating Institutions - Institute of Inorganic Chemistry ...

HIGHLIGHTS OF THE IIC SCIENCE
The scientific activity of the Institute of Inorganic Chemistry is concentrated to the
fundamental, applied and industry oriented research of the inorganic systems suitable for
design of new materials and/or technologies. Presented in the following pages are brief
summaries of recent scientific highlights.
New theoretical approaches for relativistic calculations of NMR
parameters for compounds containing heavy elements
M. Repiský, S. Komorovský, P. Hrobárik, O. L. Malkina, V. G. Malkin
An accurate prediction of electronic structure and properties of compounds containing heavy
elements obligatorily requires inclusion of relativistic effects into consideration. It means that
instead of working with the Schrödinger equation one has to deal (in one way or other) with
the Dirac equation extended for treatment of many-electron systems. Nowadays it becomes a
common point that relativity has an especially immense effect on NMR shielding tensor and
indirect nuclear spin-spin coupling constants (SSCC). Often calculations of those properties
serve as a very delicate probe to test different ways of treating relativistic effects and the basis
set quality. Lately we succeeded in the development of new relativistic four-component
density functional approach based on the use of restricted magnetically balanced basis
(mDKS-RMB) for calculations of NMR shielding [1]
and indirect nuclear spin-spin coupling constants [2]. The
unperturbed equations are solved with the use of a
restricted kinetically balanced basis set for the small
component, while to solve the second-order coupled
perturbed DKS equations a restricted magnetically
balanced basis set for the small component is applied.
The method provides an attractive alternative to existing
approximate two-component methods with transformed
Hamiltonians for relativistic calculations of spin-spin
coupling constants of heavy-atom systems. In particular,
no picture-change effects arise in our method for
property calculations. Pilot benchmark relativistic
calculations show a high reliability of the mDKS-RMB
methods. Recently, this method was extended to include
GIAO (Gauge Including Atomic Orbitals) formalism.
Our new method increases the accuracy in calculations
of NMR and EPR parameters of compounds containing
even as heavy elements as lanthanides or actinides.
Further information: V. Malkin:
vladimir.malkin@savba.sk
1. Komorovský S., Repiský M., Malkina O. L., Malkin V. G., Malkin Ondik I., Kaupp M.: J. Chem.
Phys. 128, 104101-1-104101-15, 2008
2. Repiský M., Komorovský S., Malkina O. L., Malkin V. G.: Chem. Phys. 356, 236-242, 2009
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