Ab initio study of the individual interaction energy components in the ground state of the mercury dimer

Christian Kunz, Christof Hättig, and Bernd Artur Heß
Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstr. 12, D-53115 Bonn, Germany

Mol. Phys. 89, 139-156 (1996)
(Received 2 January 1997; accepted 8 February 1996)

Relativistic and non-relativistic all-electron, ab initio methods are used to investigate the role of the individual energy components in the total interaction energy involved in the formation of the weakly bound ground state X 1Sigma+g of the Hg2 molecule. The interaction energy is partitioned according to a hybrid approach into a supermolecular repulsive potential and the damped dispersion energy derived from perturbation theory. Both parts are then computed individually and their dependence on relativity and electron correlation is investigated. From this analysis, hybrid potentials that comprise different physical interactions are constructed and the importance of specific features is evaluated by comparison of the appropriate hybrid potentials with each other and with the experimental curve. The most detailed model is based on a CASSCF supermolecular potential to which the damped intramonomer correlated dispersion energy series is added. In the relativistic case it yields a potential with quantitatively correct asymptotic behaviour and which is able to predict potential parameters that agree reasonably well with the experimental results. The asymptotic density method developed by Duman and Smirnow was tested as an inexpensive alternative for the calculation of the repulsive part of the hybrid potential. In spite of its recent success in the calculation of the He-He potential, it cannot provide a good repulsive component in the case of Hg2. As a result of this work, this failure can attributed to the unusually strong induction effects in the ground state mercury dimer bond, which lower repulsive forces substantially.

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