Effects of the basis set and of the exchange–correlation functional on the Inelastic Electron Tunneling signatures of 1,4-benzenedithiol

Abstract

The effects of the atomic basis set and of the exchange–correlation (XC) functional on the Inelastic Electron Tunneling (IET) spectra have been investigated by considering the prototypical 1,4-benzenedithiol molecule. These studies have been completed by tackling the reliability of the same methods for predicting the IR absorption spectrum of the same molecule. The main conclusions are (i) the B3LYP XC functional is suitable to predict the relative vibrational frequencies, (ii) provided a scaling factor is used, the root mean square error on the vibrational frequencies goes down to 18cm−1, (iii) triple-ζ basis sets and in particular the cc-pVTZ basis set is a good compromise between accuracy and computational needs, (iv) basis set effects on the IET intensities are larger than those of the XC functional, and (v) the cc-pVTZ, cc-pVQZ, and aug-cc-pVDZ basis sets provide consistent IET intensities.