Electric Field and Temperature Effects on the Ab Initio Spectroscopy of Liquid Methanol

Abstract

Although many H-bonded systems have been extensively investigated by means of infrared (IR) spectroscopy, the vibrational response to externally applied electric fields of polar liquids remains poorly investigated. However, local electric fields along with quantum-mechanical interactions rule the behavior of H-bonded samples at the molecular level. Among the many H-bonded systems, liquid methanol holds a key place in that it exhibits a very simple H-bond network where, on average, each molecule acts as a single H-bond donor and, at the same time, as a single H-bond acceptor. Here we report on the IR spectra emerging from a series of state-of-the-art ab initio molecular dynamics simulations of bulk liquid methanol under the action of static and homogeneous electric fields. In addition, the same analysis is here conducted in the absence of the external field and for different temperatures. Although some electric-field-induced effects resemble the response of other polar liquids (such as the global contraction of the IR spectrum upon field exposure), it turns out that, distinctly from water, the “electrofreezing” phenomenon is unlikely to happen in liquid methanol. Finally, we provide atomistic analyses magnifying the completely different nature of electric-field- and temperature-induced effects on bulk liquid methanol and on its vibrational response.