# 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} }

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…

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## References

SHOWING 1-10 OF 55 REFERENCES

### Fundamental vibrational frequencies of small polyatomic molecules from density-functional calculations and vibrational perturbation theory

- Chemistry, Physics
- 2003

An extensive study of fundamental frequencies and anharmonic vibrational constants for polyatomic molecules obtained from Becke three parameter Lee–Yang–Parr (B3LYP) and Becke–Perdew (BP86) density…

### The performance of a family of density functional methods

- Chemistry
- 1993

The results of a systematic study of molecular properties by density functional theory (DFT) are presented and discussed. Equilibrium geometries, dipole moments, harmonic vibrational frequencies, and…

### Tables of molecular vibrational frequencies. Consolidated volume II

- Chemistry
- 1972

The compilations of fundamental vibrational frequencies of molecules previously published as Tables of Molecular Vibrational Frequencies Part 5, Part 6, Part 7, and Part 8, which appeared in the…

### Harmonic Vibrational Frequencies: Scaling Factors for HF, B3LYP, and MP2 Methods in Combination with Correlation Consistent Basis Sets

- Chemistry
- 2004

A least-squares approach has been used to determine multiplicative scaling factors for harmonic vibrational frequencies to facilitate comparison with experimentally observed frequencies. The harmonic…

### Prediction of accurate anharmonic experimental vibrational frequencies for water clusters, (H2O)n, n=2-5.

- ChemistryThe journal of physical chemistry. A
- 2006

The combination of using HF/6-31G* scaled frequencies for intramolecular modes and anharmonic frequencies for intermolescular modes gives excellent agreement with experiment for the water dimer and trimer and are as good as the expensive anharmonics MP2 calculations.

### Vibrational zero-point energies and thermodynamic functions beyond the harmonic approximation.

- PhysicsThe Journal of chemical physics
- 2004

This paper compares harmonic and anharmonic zero-point energies and thermodynamic functions for a number of molecules of small and medium size using the Becke three parameter Lee-Yang-Parr functional, medium size basis sets, and, when needed, proper treatment of internal rotations.

### Potential-energy functions of diatomic molecules of the noble gases I. Like nuclear species

- Physics, Chemistry
- 1992

### Assessing the reliability of calculated catalytic ammonia synthesis rates

- ChemistryScience
- 2014

A general method for estimating the uncertainty in calculated materials properties based on density functional theory calculations is introduced and an approach for incorporating uncertainty when searching for improved catalysts by evaluating the probability that a given catalyst is better than a known standard is introduced.

### Vibrational frequency scale factors for density functional theory and the polarization consistent basis sets

- ChemistryJ. Comput. Chem.
- 2012

For this family of basis sets, the scale factors for each property are more dependent on the functional selection than on basis set level, and thus allow for a suggested scale factor for each density functional when employing polarization consistent basis sets.