Margaret Berrens^1*, Arpan Kundu², Marcos F. Calegari Andrade³, Tuan Anh Pham³, Giulia Galli^2,4,5, Davide Donadio⁶

1 Department of Chemistry, University of California Davis, Davis, CA, U.S.A

2 Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, U.S.A.

3 Quantum Simulations Group, Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, U.S.A.

4 Materials Science Division and Center for Molecular Engineering Argonne National Laboratory, Chicago, IL, U.S.A.

5 Department of Chemistry, University of Chicago, Chicago, IL, U.S.A.

6 Department of Chemistry, University of California Davis, Davis, CA, U.S.A.

* Corresponding authors emails: mlberrens@ucdavis.edu

DOI10.24435/materialscloud:pd-j6 [version v1]

Publication date: Jun 17, 2024

How to cite this record

Margaret Berrens, Arpan Kundu, Marcos F. Calegari Andrade, Tuan Anh Pham, Giulia Galli, Davide Donadio, Nuclear quantum effects on the electronic structure of water and ice, Materials Cloud Archive 2024.89 (2024), https://doi.org/10.24435/materialscloud:pd-j6

Description

The electronic properties and optical response of ice and water are intricately shaped by their molecular structure, including the quantum mechanical nature of hydrogen atoms. Despite numerous former studies, a comprehensive understanding of nuclear quantum effects (NQE) on the electronic structure of water and ice at finite temperatures remains elusive. Here, we utilize molecular simulations that harness efficient machine-learning potentials and many-body perturbation theory to assess how NQEs impact the electronic bands of water and hexagonal ice. By comparing path-integral and classical simulations, we find that NQEs lead to a larger renormalization of the fundamental gap of ice, compared to that of water, ultimately yielding similar bandgaps in the two systems, consistent with experimental estimates. Our calculations suggest that the increased quantum mechanical delocalization of protons in ice, relative to water, is a key factor leading to the enhancement of NQEs on the electronic structure of ice.

Materials Cloud sections using this data

Files

File name	Size	Description
README.txt MD5md5:57ba4c0bafe626fcd9322d85aae6d9f0	1.1 KiB	Summary of content
NQE_Repository.zip MD5md5:f9fdfedbe2e584b59de66a47dcdda5ff	16.1 MiB	This folder contains the input and starting files for the paper 'Nuclear Quantum Effects on the Electronic Structure of Water and Ice' including starting files for the classical and quantum simulations using lammps and i-pi with the NEP and DNNP, starting files for electronic structure calculations using CP2K with the revPBE0 functional, Qbox with the SCAN functional, and WEST

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External references

Keywords

electronic structure molecular dynamics water nuclear quantum effects