Soft experimental constraints for soft interactions: a spectroscopic benchmark data set for weak and strong hydrogen bonds

Abstract

Experimental data for hydrogen-bonded complexes between a small set of test molecules are converted into a benchmark set for quantum chemistry predictions in the convenient harmonic approximation.

Rotational Spectrum and Conformational Analysis of Perillartine: Insights into the Structure–Sweetness Relationship

“…Thus, we obtained scale factors by dividing the experimental rotational constants by the calculated ones; the scale factors ranged from 0.971 to 1.020, which brings the Density-functional theory (DFT) predicted values of the rotational constants into coincidence with the experimental ones. This remarkable theoretical-experimental synergy has been found in previous rotational studies [ 27 , 53 ] and is in the context of a recent spectroscopic benchmark database [ 54 ]. The observation of all the low-energy species (the four representative conformers) further supports the global consistency of the conformational assignment.…”

Understanding benzyl alcohol aggregation by chiral modification: the pairing step

“…This is reminiscent of a broader benchmark for hydrogen bonding. 77 It would be rewarding to have a functional which makes better shift predictions for hydrogen bonds without losing predictive power for the energetics of competing isomers.…”

CC-stretched formic acid: isomerisation, dimerisation, and carboxylic acid complexation

“…This good performance of harmonic vibrational frequency calculations at the B3LYP-D3(BJ) level for relative quantities has been observed for other carboxylic acids 30,52,87 and various other hydrogen bonded clusters. 88 In the following section, dimerisation of trans-propiolic acid shall be explored. As seen in Fig.…”