Equilibrium structure in the presence of internal rotation: A case study of cis-methyl formate

• Published in: Journal of molecular spectroscopy 2010-02, Vol.259 (2), p.70-79
• Main Authors: Demaison, J., Margulès, L., Kleiner, I., Császár, A.G.
• Format: Article
• Language: English
• Subjects: Ab initio; Equilibrium structure; Internal rotation; Methyl formate; Semi-experimental
• ISSN: 0022-2852; 1096-083X
• DOI: 10.1016/j.jms.2009.11.007

The Born–Oppenheimer (BO) equilibrium molecular structure ( r e BO ) of cis-methyl formate has been determined at the CCSD(T) level of electronic structure theory using Gaussian basis sets of at least quadruple-ζ quality and a core correlation correction. The quadratic, cubic and semi-diagonal quartic force field in normal coordinates has also been computed at the MP2 level employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure ( r e SE ) has been derived from experimental ground-state rotational constants and the lowest-order rovibrational interaction parameters calculated from the ab initio cubic force field. To determine r e SE structures, it is important to start from accurate ground-state rotational constants. Different spectroscopic methods, applicable in the presence of internal rotation and used in the literature to obtain “unperturbed” rotational constants from the analysis and fitting of the spectrum, are reviewed and compared. They are shown to be compatible though their precision may be different. The r e BO and r e SE structures are in good agreement showing that, in the particular case of cis-methyl formate, the methyl torsion can still be treated as a small-amplitude vibration. The best equilibrium structure obtained for cis-methyl formate is: r(C m–O) = 1.434 Å, r(O–C c) = 1.335 Å, r(C m–H s) = 1.083 Å, r(C m–H a) = 1.087 Å, r(C c–H) = 1.093 Å, r(C O) = 1.201 Å, ∠ (COC) = 114.4°, ∠ (CCH s) = 105.6°, ∠ (CCH a) = 110.2°, ∠ (OCH) = 109.6°, ∠ (OCO) = 125.5°, and τ(H aCOC) = 60.3°. The accuracy is believed to be about 0.001 Å for the bond lengths and 0.1° for the angles.