A restricted-open-shell complete-basis-set model chemistry

Abstract

A restricted-open-shell model chemistry based on the complete basis set-quadratic Becke3 (CBS-QB3) model is formulated and denoted ROCBS-QB3. As the name implies, this method uses spin-restricted wave functions, both for the direct calculations of the various components of the electronic energy and for extrapolating the correlation energy to the complete-basis-set limit. These modifications eliminate the need for empirical corrections that are incorporated in standard CBS-QB3 to compensate for spin contamination when spin-unrestricted wave functions are used. We employ an initial test set of 19 severely spin-contaminated species including doublet radicals and both singlet and triplet biradicals. The mean absolute deviation (MAD) from experiment for the new ROCBS-QB3 model (3.6±1.5kJmol−1) is slightly smaller than that of the standard unrestricted CBS-QB3 version (4.8±1.5kJmol−1) and substantially smaller than the MAD for the unrestricted CBS-QB3 before inclusion of the spin correction (16.1±1.5kJmol−1). However, when applied to calculate the heats of formation at 298K for the moderately spin-contaminated radicals in the G2/97 test set, ROCBS-QB3 does not perform quite as well as the standard unrestricted CBS-QB3, with a MAD from experiment of 3.8±1.6kJmol−1 (compared with 2.9±1.6kJmol−1 for standard CBS-QB3). ROCBS-QB3 performs marginally better than standard CBS-QB3 for the G2/97 set of ionization energies with a MAD of 4.1±0.1kJmol−1 (compared with 4.4±0.1kJmol−1) and electron affinities with a MAD of 3.9±0.2kJmol−1 (compared with 4.3±0.2kJmol−1), but the differences in MAD values are comparable to the experimental uncertainties. Our overall conclusion is that ROCBS-QB3 eliminates the spin correction in standard CBS-QB3 with no loss in accuracy.