To predict the vibrational spectra of molecules, ab initio calculations are often used to compute harmonic frequencies, which are usually scaled by empirical factors as an approximate correction for errors in the force constants and for anharmonic effects. Anharmonic computations of fundamental frequencies are becoming more popular. We report scaling factors, along with their associated uncertainties, for anharmonic (second-order perturbation theory) predictions from HF, MP2, and B3LYP calculations using the 6-31G(d) and 6-31+G(d,p) basis sets. Different scaling factors are appropriate for low- and high-frequency vibrations. The method of analysis is based upon the Guide to the Expression of Uncertainty in Measurement, published by the International Organization for Standardization (ISO). The data used are from the Computational Chemistry Comparison and Benchmark Database (CCCBDB), maintained by the National Institute of Standards and Technology, which includes more than 3939 independent vibrations for 358 molecules.
Citation: Journal of Chemical Theory and Computation
Pub Type: Journals
ab initio, anharmonic, computational chemistry, density functional theory, quantum chemistry, uncertainty, vibrational frequencies, virtual measurement