The water dimer interaction energy: Convergence to the basis set limit at the correlated level
1997; American Institute of Physics; Volume: 107; Issue: 12 Linguagem: Inglês
10.1063/1.474820
ISSN1520-9032
AutoresMartin Schütz, Steve Brdarski, Per‐Olof Widmark, Roland Lindh, Gunnar Karlström,
Tópico(s)Free Radicals and Antioxidants
ResumoThe water dimer interaction energy and its convergence to the basis set limit was investigated, with electron correlation effects treated at the level of second order Mo/ller-Plesset perturbation theory (MP2). ANO-type and large uncontracted basis sets were used, spreading over a wide range in size; the biggest set included 1046 functions with angular momentum up to (l=7). Core correlation effects were treated accurately by augmenting the original valence basis with extended sets of core polarization functions. The MP2 dimer interaction energy at the basis set limit was determined to −4.94±0.02 kcal/mol, with a contribution due to core correlation of −0.04 kcal/mol. Furthermore, based on some elementary considerations from intermolecular perturbation theory, a simple procedure was devised, which brings the counterpoise corrected interaction energies of moderate basis set calculations closer to the basis set limit. The interaction energies so obtained turned out be surprisingly stable with respect to extensions of the basis set.
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