• DOI:10.1021/ACS.JPCC.8B11689
• Corpus ID: 104298456

Uncertainty Quantification in First-Principles Predictions of Harmonic Vibrational Frequencies of Molecules and Molecular Complexes

@article{Parks2018UncertaintyQI,
  title={Uncertainty Quantification in First-Principles Predictions of Harmonic Vibrational Frequencies of Molecules and Molecular Complexes},
  author={Holden L Parks and Alan J. H. McGaughey and Venkatasubramanian Viswanathan},
  journal={The Journal of Physical Chemistry C},
  year={2018}
}

• Holden L Parks, A. McGaughey, V. Viswanathan
• Published 4 December 2018
• Chemistry
• The Journal of Physical Chemistry C

Accurate prediction of molecular vibrational frequencies is important to identify spectroscopic signatures and reaction thermodynamics. In this work, we develop a method to quantify the uncertainty associated with density functional theory-predicted harmonic vibrational frequencies using the built-in error estimation capabilities of the Bayesian error estimation functional with van der Waals exchange–correlation functional. The method is computationally efficient as it estimates the uncertainty at nearly the same computational cost as a single vibrational frequency calculation. We demonstrate the utility and robustness of the method by showing that the uncertainty estimates bound the self-consistent calculations of 6 exchange–correlation functionals for 10 small molecules, 10 rare-gas dimers, and molecular complexes from the S22 dataset. The rare-gas dimers and the S22 dataset provide a rigorous test, as they are systems with complicated vibrational motion and noncovalent interactions. Using the coefficie...