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Updated: Jul 8, 2025

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy
Published on: May 27, 2018
Vibrational Spectra of Highly Anharmonic Water Clusters: Molecular Dynamics and Harmonic Analysis Revisited with
Yuzhe Zhang1, Yiwen Wang1, Xi Xu2
1Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
Abstract:
Vibrational spectroscopy is widely used to gain insights into structural and dynamic properties of chemical, biological, and materials systems. Thus, an efficient and accurate method to simulate vibrational spectra is desired. In this paper, we justify and employ a microcanonical molecular simulation scheme to calculate the vibrational spectra of three challenging water clusters: the neutral water dimer (H4O2), the protonated water trimer (H7O3+), and the protonated water tetramer (H9O4+). We find that with the accurate description of quantum nuclear delocalization effects through the constrained nuclear-electronic orbital framework, including vibrational mode coupling effects through molecular dynamics simulations can additionally improve the vibrational spectrum calculations. In contrast, without the quantum nuclear delocalization picture, conventional ab initio molecular dynamics may even lead to less accurate results than harmonic analysis.
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