Efficient Quantum Vibrational Spectroscopy of Water with High-Order Path Integrals: from Bulk to Interfaces

Abstract: Vibrational spectroscopy is key for probing the interplay between the structure and dynamics of aqueous systems. In order 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 quantum vibrational spectra of aqueous systems can be dramatically reduced compared to 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 of the infrared and Raman spectra of bulk water, but also of 2D correlation and 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 accuracy.