Extrapolating potential energy surfaces by scaling electron correlation: Isomerization of bicyclobutane to butadiene

The recently proposed potential energy surface (PES) extrapolation scheme, which predicts smooth molecular PESs corresponding to larger basis sets from the relatively inexpensive calculations using smaller basis sets by scaling electron correlation energies [A. J. C. Varandas and P. Piecuch, Chem. Phys. Lett. 430, 448 (2006)], is applied to the PESs associated with the conrotatory and disrotatory isomerization pathways of bicyclo [1.1.0] butane to buta-1,3-diene. The relevant electronic structure calculations are performed using the completely renormalized coupled-cluster method with singly and doubly excited clusters and a noniterative treatment of connected triply excited clusters, termed CR-CC (2,3), which is known to provide a highly accurate description of chemical reaction profiles involving biradical transition states and intermediates. A comparison with the explicit CR-CC (2,3) calculations using the large correlation- consistent basis set of the cc-pVQZ quality shows that the cc-pVQZ PESs obtained by the extrapolation from the smaller basis set calculations employing the cc-pVDZ and cc-pVTZ basis sets are practically identical, to within fractions of a millihartree, to the true cc-pVQZ PESs. It is also demonstrated that one can use a similar extrapolation procedure to accurately predict the complete basis set (CBS) limits of the calculated PESs from the results of smaller basis set calculations at a fraction of the effort required by the conventional pointwise CBS extrapolations. (C) 2008 American Institute of Physics.