Accurate bond dissociation energy of water determined by triple-resonance vibrational spectroscopy and ab initio calculations

An Evaluation of Gas Phase Enthalpies of Formation for Hydrogen-Oxygen (HxOy) Species

“…The selected value is in excellent agreement with the high level quantum calculations of Boyarkin et al (2013) [76] (within 8 cm −1 or 0.1 kJ mol −1 -the estimated uncertainty in the calculations). The range of other quantum calculations given in Table 3 are almost as good, providing values within about 0.3 kJ mol −1 of the selected value.…”

“…The selected value of the gas phase enthalpy of formation of OH is derived from the experimental work of Boyarkin et al (2013) [76] and Maksyutenko et al (2006) [77] [9] have evaluated the enthalpy of formation for OH using a thermochemical network approach using these two measurements and other input data and recommend a value that is within the uncertainties of the direct experimental determinations.…”

Perspective: Accurate ro-vibrational calculations on small molecules

“…114,165 These experiments have the major advantage over the neardissociation experiments on H + 3 that their multiphoton nature both greatly simplifies the resulting spectrum and makes the assignment of the rotational quantum numbers to the final state relatively straightforward. Variational calculations on the bound levels gives good general agreement 166 with the observations although the differences increase markedly just below dissociation suggesting that the PES in this region is less accurate than at lower energies.…”

“…Moving further up the energy levels, Boyarkin, Rizzo and co-workers performed a series of multi-photon experiments which probed rotation-vibration levels of water below, [159][160][161][162][163] above 114,164 and, indeed, at dissociation. 114,165 These experiments have the major advantage over the neardissociation experiments on H + 3 that their multiphoton nature both greatly simplifies the resulting spectrum and makes the assignment of the rotational quantum numbers to the final state relatively straightforward.…”

“…Examples are given in the papers cited elsewhere in this perspective. [109][110][111][112][113][114] Of course, for simpler systems with fewer electrons, more of these effects can be included in the base calculation; for example, starting from an all-electron calculation eliminates the need to consider separately correlation of the core electrons.…”