Vibrational mode frequency correction of liquid water in density functional theory molecular dynamics simulations with van der Waals correction
Literature Information
Chun-Chieh Yu, Mayank Dodia, Mischa Bonn, Yuki Nagata, Tatsuhiko Ohto
The frequencies and spectral lineshapes of the stretch and bending modes of water provide invaluable information on the microscopic structures of water in aqueous solutions and at the water/solid interfaces. Density functional theory molecular dynamics (DFT-MD) simulation has been used not only for predicting the properties of water but also for interpreting the vibrational spectra of water. Since the accuracy of the DFT-MD simulations relies on the choice of the exchange–correlation functionals and dispersion correction schemes employed, the predicted vibrational spectra at different levels of DFT theory differ significantly, prohibiting precise comparison of simulated spectra with experimental data. Here, we simulate the vibrational density of states for liquid heavy water based on various DFT-MD trajectories. We find that DFT-MD simulations tend to predict excessive inhomogeneous broadening for the stretch mode of water. Furthermore, we develop a frequency correction scheme for the stretch and bending modes of liquid water, which substantially improves the prediction of the vibrational spectra.
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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