F12-TZ-cCR: A Methodology for Faster and Still Highly Accurate Quartic Force Fields

The F12-TZ-cCR quartic force field (QFF) methodology, defined here as CCSD(T)-F12b/cc-pCVTZ-F12 with further corrections for relativity, is introduced as a cheaper and even more accurate alternative to more costly composite QFF methods like those containing complete basis set extrapolations within canonical coupled cluster theory. F12-TZ-cCR QFFs produce B-0 and C-0 vibrationally averaged principal rotational constants within 7.5 MHz of gas-phase experimental values for tetraatomic and larger molecules, offering higher accuracy in these constants than the previous composite methods. In addition, F12-TZ-cCR offers an order of magnitude decrease in the computational cost of highly accurate QFF methodologies accompanying this increase in accuracy. An additional order of magnitude in cost reduction is achieved in the F12-DZ-cCR method, while also matching the accuracy of the traditional composite method's B-0 and C-0 constants. Finally, F12-DZ and F12-TZ are benchmarked on the same test set, revealing that both methods can provide anharmonic vibrational frequencies that are comparable in accuracy to all three of the more expensive methodologies, although their rotational constants lag behind. Hence, the present work demonstrates that highly accurate theoretical rovibrational spectral data can be obtained for a fraction of the cost of conventional QFF methodologies, extending the applicability of QFFs to larger molecules.

Automated summary

The F12-TZ-cCR methodology offers a cheaper and more accurate alternative to composite QFF methods, providing higher accuracy in rotational constants while significantly reducing computational costs. The F12-DZ-cCR method further decreases costs while maintaining accuracy, demonstrating the potential for highly accurate theoretical spectral data at a fraction of the cost compared to traditional methods.