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

• Determination of equilibrium structure of thymine from MW rotational constants.
• Computation of rovibrational corrections from cubic MP2/cc-pVTZ force field.
• CCSD(T)(AE) structure optimization with extrapolation to cc-pwCVQZ basis set.
• Observation of methylation effect on the structure of uracil.
• Discussion of the poor behavior of Kraitchman’s equations.

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 0.002 Å 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.

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