Classical nuclear motion: Does it fail to explain reactions and spectra in certain cases?

Abstract

AbstractIs a classical description of nuclear motion sufficient when describing chemical reactions and spectra? This question is interesting because many researchers use a classical description of nuclear motion in molecular dynamics simulations. The present paper investigates some phenomena that were previously attributed to nuclear quantum effects. The question is if these phenomena can be modeled with traditional Car–Parrinello molecular dynamics, that is, with a method which treats nuclear motion classically and which is widely applied to the simulation of chemical reactions and spectra. We find that for the investigated system no additional paradigm is needed for describing chemical reactions. The special reactivity observed for carbenes can be attributed to the special environment represented by a noble gas matrix and to an additional transition state that was not considered before. Also the infrared spectrum of porphycene is perfectly modeled by traditional Car–Parrinello molecular dynamics. More studies are necessary to decide to what extent classical nuclear motion can replace the quantum mechanical description.