Modeling electronic absorption spectra with nuclear quantum effects in constrained nuclear–electronic orbital framework

Abstract

Electronic absorption spectra serve as versatile and powerful tools in experiments. Accurate theoretical simulation of electronic absorption spectra is challenging because multiple factors such as environmental effects and nuclear quantum effects contribute to spectrum lineshapes. This work proposes a protocol to model electronic absorption spectra in the constrained nuclear–electronic orbital framework. Solvent effects, temperature effects, and particularly nuclear quantum effects can be taken into consideration in this unified framework. This protocol is applied to investigate the electronic absorption spectrum of the pyridine molecule in water. Nuclear quantum effects are found to induce a broadening and red shift of the absorption spectrum of pyridine.