2017/02/24 by Ondrej Marsalek, Ondřej Maršálek, Thomas E. Markland +2 · 17 citations
Chemistry · Physics and Astronomy · #Ab initio #Advanced Chemical Physics Studies #Aqueous solution #Chemical Physics (physics.chem-ph) #Chemical physics #Chemistry #Computational chemistry #Density functional theory #Electron #Electron spectroscopy #Electronic structure #FOS: Physical sciences #Molecular dynamics #Molecule #Physical chemistry #Physics #Quantum #Quantum chemistry #Quantum mechanics #Quantum, superfluid, helium dynamics #Raman spectroscopy #Reactivity (psychology) #Spectroscopy #Spectroscopy and Quantum Chemical Studies #Statistical Mechanics (cond-mat.stat-mech) #cond-mat.stat-mech #physics.chem-ph
paper · pdf · doi:10.48550/arxiv.1702.07797
published in arXiv (Cornell University) (Cornell University)
arxiv created 2017/02/24 · openalex publication_date 2017/02/24 · arxiv updated 2017/02/28 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
Understanding the reactivity and spectroscopy of aqueous solutions at the atomistic level is crucial for the elucidation and design of chemical processes. However, the simulation of these systems requires addressing the formidable challenges of treating the quantum nature of both the electrons and nuclei. Exploiting our recently developed methods that provide acceleration by up to two orders of magnitude, we combine path integral simulations with on-the-fly evaluation of the electronic structure at the hybrid density functional theory level to capture the interplay between nuclear quantum effects and the electronic surface. Here we show that this combination provides accurate structure and dynamics, including the full infra-red and Raman spectra of liquid water. This allows us to demonstrate and explain the failings of lower-level density functionals for dynamics and vibrational spectroscopy when the nuclei are treated quantum mechanically. These insights thus provide a foundation for the reliable investigation of spectroscopy and reactivity in aqueous environments.