Benchmarking the quadrupolar coupling tensor for chlorine to probe weak-bonding interactions

Abstract

Rotational spectroscopy relies on quantum chemical calculations to interpret observed spectra. In this context, among the most challenging molecules to assign are those with many additional angular momenta coupling to...

Weak hydrogen bonding to halogens and chirality communication in propanols: Raman and microwave spectroscopy benchmark theory

“…The seemingly good performance of the GGAs may be related to error compensation from projection of the electric field gradient to the inertial principal axis system. 98 Considering all properties studied in this work, only CCSD(T) is seen to perform consistently well after estimating anharmonic and relativistic effects, confirming its ''gold standard'' reputation. Harmonic B3LYP has a favourable priceperformance ratio, but we demonstrate several cases of fortuitous error cancellation.…”

“…The seemingly good performance of the GGAs may be related to error compensation from projection of the electric field gradient to the inertial principal axis system. 98…”

“…We expect that coupled cluster is more accurate than Bailey's method. 98 This journal is © the Owner Societies 2024…”

“…It should also be kept in mind that although the electric field gradient might be predicted correctly by a given method, the projection to the inertial principal axis system may introduce deviations from experiment. 98 This may lead to error compensation or error compounding. The results are shown in Fig.…”

“…Uncertainties are based on a and b. We expect that coupled cluster is more accurate than Bailey's method 98.…”