Dresden 2011 – scientific programme
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MO: Fachverband Molekülphysik
MO 2: Theory: Quantum Chemistry and Molecular Dynamics
MO 2.8: Talk
Monday, March 14, 2011, 12:15–12:30, MER 02
Theory corroborates experiment: a relativistic study of the isotopic field shift in rotational spectra — •Stefan Knecht1 and Trond Saue2 — 1Institut for Fysik og Kemi, Syddansk Universitet, Odense, Danmark — 2Laboratoire de Physique Quantique, CNRS/Université Paul Sabatier, Toulouse, France
A number of distinctive molecular properties such as the nuclear magnetic resonance shielding parameters, Mössbauer isomer shifts and isotopic field shift probe the electronic density near the nuclei. Their appealing feature is that they provide local information at a nuclear center with great sensitivity to the chemical environment.
Here, we present accurate theoretical estimates of the isotopic field shift in rotational spectra of lead chalcogenides PbX (X=S,Se,Te) and thallium halides TlY (Y=F,Cl,Br,I) derived from 4-component relativistic Coupled-Cluster and Density Functional Theory calculations. We compare our findings [1] with the early experimental work [2,3] on this correction term to the Dunham coefficient Y01, which is due to a finite nuclear charge distribution, as well as with other theoretical predictions [4]. It is highlighted that a sophisticated relativistic approach is required to achieve an excellent agreement with the experiment.
[1] S. Knecht and T. Saue, in preparation (2010).
[2] J. Schlembach and E. Tiemann, Chem. Phys. 68 (1982) 21.
[3] H. Knöckel, T. Kröckertskothen, and E. Tiemann, Chem. Phys. 93 (1985) 349.
[4] K. C. Etchison, C. T. Dewberry, and S. A. Cooke, Chem. Phys. 342 (2007) 71.