Premium
Theoretical Investigation of Clusters of Phosphorus and Arsenic: Fascination and Temptation of High Symmetries
Author(s) -
Nava Paola,
Ahlrichs Reinhart
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200701927
Subject(s) - temptation , arsenic , phosphorus , homogeneous space , psychology , chemistry , mathematics , social psychology , organic chemistry , geometry
Abstract We present a theoretical study of the energetic and thermodynamic stability of selected phosphorus and arsenic clusters containing 18 to 168 atoms. For this purpose we employ MP2 as well as DFT functionals BP86 and B3LYP with extended basis sets. All procedures predict the family of one‐dimensional polymers X 18+12 n , each with 2 n −1 isomers of virtually identical energy, to be more stable than other structures investigated so far. Furthermore, islands of stability result for ring‐shaped clusters X 24 n with D nd symmetry for n =4 (only for arsenic), 5, 6, and 7. Phosphorus and arsenic show otherwise a very similar behavior. An investigation of basis set effects shows that a doubly polarized triple zeta valence basis (TZVPP) is both necessary and sufficient. In comparison to the reliable spin component scaled MP2 (SCS‐MP2) procedure, DFT methods underestimate and MP2 overestimates the stability of larger clusters; the discrepancy increases with the number of atoms. The addition of a long‐range dispersion correction to B3LYP energies does not rectify the shortcomings of DFT in comparison with SCS‐MP2.