The equilibrium OH bond length

Abstract

The equilibrium structure of 36 small molecules containing OH bonds, including molecules with an internal hydrogen bond, is reviewed from the literature. The structures are redetermined or determined, if necessary, using high level ab initio calculations at the CCSD(T) level of theory with basis sets of quintuple zeta quality and with a correction for the core correlation. The possibility of calculating accurate ab initio OH bond lengths at different levels of theory (MP2/VTZ, MP2/VQZ, CCSD(T)/VTZ, and CCSD(T)/AVTZ) is examined. All methods agree provided a small offset correction is taken into account. In most cases, the addition of diffuse functions does not improve the results. The MP2 method appears to be satisfactory whenever the non-dynamical electron correlation is small, which is the most typical situation. The various results are merged to demonstrate the following quantitative correlation between r e(OH) and ‘isolated’ OH stretching frequencies, relevant for predictive use: r e(OH) [Å] = 1.2261(76)–7.29(21) × 10−5 νis(OH) [cm−1].