Theoretical study of electronic structure and spectroscopy of molecules containing metallic atoms

• Main Author: Hayashi, Shinsuke
• Language: English
• Published: Université Paris-Est 2008
• Subjects: [CHIM] Chemical Sciences; [CHIM] Chimie; Metallic atom; Relativistic effect; Close lying states; Piezoelectricity; Isotopes and vibrational spectrum
• Online Access: http://tel.archives-ouvertes.fr/tel-00462184; http://tel.archives-ouvertes.fr/docs/00/46/21/84/PDF/2008PEST0216_0_0.pdf

In this work we have investigated the electronic properties of several types of molecular systems involving a metallic element. Our motivation for such applications on metallic compounds was to obtain an accurate description of close lying electronic states, in which the relativistic effects of heavy atoms are known to be important. Thus various approaches and methods have been employed to treat these effects, including the multi-configurational method, with atomic pseudopotentials and large basis sets. In the first study, we have determined the properties of the low lying electronic states of the diatomic compounds MX, whose combinations in the solid phase produce ionic semi-conductor materials with piezoelectric properties. Based on highly correlated ab initio calculations, we have elucidated the common properties of the low lying electronic states of these diatomic compounds with eight valence electrons, which can be considered as precursors for piezoelectric effects in their solid phase. Based on our electronic structure calculations, we could identify among these diatomic compounds those who could lead to good candidates for piezoelectric effects. As the second application, we have determined the electronic structure and the spectroscopic constants for the ground state of the HZnF molecule and for the low lying electronic states of its diatomic fragments. This application was initiated and motivated by interesting and puzzling results on the close system HZnCl. Comforted by our experience with the previous studies, we used the pseudopotentials approach to obtain an accurate description of the low lying states of ZnH which could be satisfactorily compared with existing data. Next, the ZnF and ZnCl diatomic molecules have been studied with the same ansatz to reveal the properties of so far unknown electronic states. Finally, the potential energy surface of the ground state of HZnF has been determined, and several spectroscopic properties have been deduced