Nuclear size effects in rotational spectra: A tale with a twist
- 作者：Stefan Knechta ; knecht@ifk.sdu.dk ; Trond Saueb ; trond.saue@irsamc.ups-tlse.fr
- 关键词：Relativistic quantum chemistry ; Nuclear size effects ; Diatomic molecules ; Contact electron density ; Molecular properties
- 刊名：Chemical Physics
- 出版年：2012
- 期刊代码：18_03010104
- 类别：ch
- 出版时间：5 June, 2012
- 卷：401
- 期：Complete
- 页码：103-112
- 文件大小：417 K
摘要
We report a 4-component relativistic benchmark study of the isotopic field shift in the rotational spectrum of three diatomic molecules: TlI, PbTe and PtSi. A central quantity in the theory is the derivative with respect to internuclear distance of an effective electron density associated with a given nucleus, calculated at the equilibrium distance. The effective density, which is related to the mean electron density within the nuclear volume, is usually replaced with the contact density, that is, the electron density at the origin of the nucleus. Our computational study shows that for the chosen systems this induces errors on the order of 10%, which is not acceptable for high-precision work. On the other hand, the systematic nature of the error suggests that it can be handled by an atom-specific correction factor. Our calibration study reveals that relativistic effects increase the contact density gradient by about an order of magnitude, and that the proper transformation of the associated property operator is mandatory in 1- and 2-component relativistic calculations. Our results show very good agreement with the experimental data presented by Schlembach and Tiemann [Chem. Phys. 68 (1982) 21], but disagree completely with the revised results given by the same group in a later paper [Chem. Phys. 93 (1985) 349]. We have carefully re-derived the relevant formulas and cannot see that the rescaling of results is justified. Curiously previous DFT calculations agree quite well with the revised results for TlI and PbTe, but we demonstrate that this is because the authors inadvertently employed a non-relativistic Hamiltonian, which by chance induces an error of the same magnitude as the suggested scaling. For the PtSi molecule our results for the correction term due to nuclear volume disagree with experiment by a factor five, and we recommend a re-examination of the experimental data.