How well can RMP4 theory treat homolytic fragmentations?
1988; Elsevier BV; Volume: 148; Issue: 6 Linguagem: Inglês
10.1016/0009-2614(88)80328-2
ISSN1873-4448
AutoresPeter M. W. Gill, Ming Wah Wong, Ross H. Nobes, Leo Radom,
Tópico(s)Quantum, superfluid, helium dynamics
ResumoThe observation that fourth-order restricted Møller-Plesset perturbation theory (RMP4) gives a satisfactory description of the He22+ potential curve up to the transition structure for dissociation has led to a general examination of the applicability of RMP4 theory to the study of homolytic fragmentation in dications. It appears that, in many cases, RMP4 energies do indeed provide a useful estimate of the barrier height impeding such fragmentations and that the barrier may be estimated economically by calculating RMP4 single-point energies on the UMP2 geometries of the equilibrium and transition structures. We propose the use of a new quantity, the Λ parameter, as an approximate measure of the rate of convergence of the RMP perturbation series and hence of the reliability of RMP4 energies.
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