Biological and Chemical Physics


A hierarchical family of five three-dimensional potential energy surfaces has been developed for the benchmark He-CO system. Four surfaces were obtained at the coupled cluster singles and doubles level of theory with a perturbational estimate of triple excitations, CCSD(T), and range in quality from the doubly augmented double-zeta basis set to the complete basis set (CBS) limit. The fifth corresponds to an approximate CCSDT/CBS surface (CCSD with iterative triples/CBS, denoted CBS+corr). The CBS limit results were obtained by pointwise basis set extrapolations of the individual counterpoise-corrected interaction energies. For each surface, over 1000 interaction energies were accurately interpolated using a reproducing kernel Hilbert space approach with an R-6+R-7asymptotic form. In each case, both three-dimensional and effective two-dimensional surfaces were developed. In standard Jacobi coordinates, the final CBS+corr surface has a global minimum at rCO=2.1322a0, R=6.418a0, and γ=70.84° with a well depth of -22.34 cm-1. The other four surfaces have well depths ranging from -14.83 cm-1 [CCSD(T)/d-aug-cc-pVDZ] to -22.02 cm-1 [CCSD(T)/CBS]. For each of these surfaces the infrared spectrum has been accurately calculated and compared to experiment, as well as to previous theoretical and empirical surfaces. The final CBS+corr surface exhibits root-mean-square and maximum errors compared to experiment (4He) of just 0.03 and 0.04 cm-1, respectively, for all 42 transitions and is the most accurate ab initio surface to date for this system. Other quantities investigated include the interaction second virial coefficient, the integral cross sections, and thermal rate coefficients for rotational relaxation of CO by He, and rate coefficients for CO vibrational relaxation by He. All the observable quantities showed a smooth convergence with respect to the quality of the underlying interaction surface.

Original Citation

Kirk A. Peterson and George C. McBane. A hierarchical family of three dimensional potential energy surfaces for He–CO. J. Chem. Phys., 123(8):084314, 2005. (Erratum in J. Chem. Phys., 124(22):229901, 2006.).