Article,
Chemical accuracy in ab initio thermochemistry and spectroscopy: current strategies and future challenges
Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), 131 (1): 1-20 (January 2012)
DOI: 10.1007/s00214-011-1079-5
Abstract
The current state of the art in wavefunction-based electronic structure methods is illustrated via discussions of the most important effects incorporated into a selection of high-accuracy methods chosen from the chemical literature. If one starts with a high-quality correlation treatment, such as provided by the CCSD(T) coupled cluster method, the leading effects include convergence of the results with respect to the 1-particle basis set, (outer)core/valence correlation, scalar relativistic effects and a number of smaller effects. For thermochemical properties such as the heat of formation, the zero-point vibrational energy also becomes important, introducing its own set of difficulties to the computational approach. Changes in the various components as the chemical systems incorporate heavier elements and as the size of the systems grows are also considered. Finally, challenges arising from the desire to extend existing methods to transition metal and heavier elements are considered.
