Efficient Quantum Vibrational Spectroscopy of Water with HighOrder Path Integrals: From Bulk to Interfaces

Samuel Shepherd, Jinggang Lan, David M. Wilkins*, Venkat Kapil

*Corresponding author for this work

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Vibrational spectroscopy is key in probing the interplay between the structure and dynamics of aqueous systems. To map different regions of experimental spectra to the microscopic structure of a system, it is important to combine them with first-principles atomistic simulations that incorporate the quantum nature of nuclei. Here we show that the large cost of calculating the quantum vibrational spectra of aqueous systems can be dramatically reduced compared with standard path integral methods by using approximate quantum dynamics based on high-order path integrals. Together with state-of-the-art machine-learned electronic properties, our approach gives an excellent description not only of the infrared and Raman spectra of bulk water but also of the 2D correlation and the more challenging sum-frequency generation spectra of the water–air interface. This paves the way for understanding complex interfaces such as water encapsulated between or in contact with hydrophobic and hydrophilic materials through robust and inexpensive surface-sensitive and multidimensional spectra with first-principles accurac
Original languageEnglish
Pages (from-to)9108-9114
Number of pages7
JournalJournal of Physical Chemistry Letters
Early online date15 Sep 2021
Publication statusEarly online date - 15 Sep 2021


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