A benchmark study of molecular structure by experimental and theoretical methods: Equilibrium structure of thymine from microwave rotational constants and coupled-cluster computations

Abstract

Accurate equilibrium, re, structures of thymine have been determined using two different, and to some extent complementary techniques. The composite ab initio Born–Oppenheimer, re(best ab initio), structural parameters are obtained from the all-electron CCSD(T) and MP2 geometry optimizations using Gaussian basis sets up to quadruple-zeta quality. The semi-experimental mixed estimation method, where internal coordinates are fitted concurrently to equilibrium rotational constants and geometry parameters obtained from a high level of electronic structure theory. The equilibrium rotational constants are derived from experimental effective ground-state rotational constants and rovibrational corrections based on a quantum-chemical cubic force field. Equilibrium molecular structures accurate to 0.002Å and 0.2° have been determined. This work is one of a few accurate equilibrium structure determinations for large molecules. The poor behavior of Kraitchman’s equations is discussed.