On the stability of Be3: A benchmark complete active space self-consistent field + averaged quadratic coupled cluster study

J. I. Amaro-Estrada , Anthony Scemama (1) , Michel Caffarel (1) , Alejandro Ramirez-Solis

1 GMO - Groupe THEO (LCPQ)

The optimized geometries and binding energies for the linear and triangular isomers of the beryllium trimer have been obtained through benchmark multireference averaged quadratic coupled cluster (AQCC) calculations using very large complete active space SCF (CASSCF) references (12 active electrons in 13 and 14 orbitals). Geometries were optimized with the cc-pV5Z basis, while the binding energies (including counterpoise correction) were obtained with the significantly larger aug-cc-pV5Z basis set. The binding energies (27.3 and 16.3 kcal/mol for the equilateral and linear isomers, respectively) are larger than the previous full CI benchmark values, while the corresponding Be-Be equilibrium distances of 4.101 and 4.088 a.u. are smaller. In view of the near-size consistency character of the CASSCF + AQCC method, the fact that all 12 electrons are fully correlated, the active reference space includes 14 orbitals, and the very large basis set used here, we propose to consider these results as reference data for Be3. Using the electron pair localization function obtained at the CASSCF(12,15) level, it is clearly illustrated that the 2p orbitals lying in the molecular plane play a dominant role in the bonding pattern for the equilateral isomer.

Domaines: Chimie théorique et/ou physique

J. I. Amaro-Estrada, Anthony Scemama, Michel Caffarel, Alejandro Ramirez-Solis. On the stability of Be3: A benchmark complete active space self-consistent field + averaged quadratic coupled cluster study. Journal of Chemical Physics, 2011, 135 (10), pp.104311/1-104311/7. ⟨10.1063/1.3635403⟩. ⟨hal-00875418⟩