Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21
Abstract
The spectroscopic features of protonated water species in dilute acid solutions have been long sought after for understanding the microscopic behavior of the proton in water with gas-phase water clusters H+(H2O)n extensively studied as bottom-up model systems. We present a new protocol for the calculation of the infrared (IR) spectra of complex systems, which combines the fragment-based Coupled Cluster method and anharmonic vibrational quasi-degenerate perturbation theory, and demonstrate its accuracy towards the complete and accurate assignment of the IR spectrum of the H+(H2O)21 cluster. The site-specific IR spectral signatures reveal two distinct structures for the internal and surface four-coordinated water molecules, which are ice-like and liquid-like, respectively. The effect of inter-molecular interaction between water molecules is addressed, and the vibrational resonance is found between the O-H stretching fundamental and the bending overtone of the nearest neighboring water molecule. The revelation of the spectral signature of the excess proton offers deeper insight into the nature of charge accommodation in the extended hydrogen-bonding network underpinning this aqueous cluster.
- Authors:
-
[1];
[3];
[4];
[5];
[6]
- China Pharmaceutical Univ., Nanjing (China); East China Normal Univ., Shanghai (China). Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development
- East China Normal Univ., Shanghai (China). Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development
- Univ. of Nebraska, Lincoln, NE (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA
- RIKEN, Saitama (Japan). Theoretical Molecular Science Laboratory
- East China Normal Univ., Shanghai (China). Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development; New York Univ. Shanghai (China). New York University-East China Normal University Center for Computational Chemistry
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences; National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China; Shanghai Municipal Natural Science Foundation; Fundamental Research Funds for China Pharmaceutical University; JSPS KAKENHI
- OSTI Identifier:
- 1830221
- Report Number(s):
- PNNL-SA-163212
Journal ID: ISSN 2041-1723
- Grant/Contract Number:
- AC05-76RL01830; AC02-05CH11231; 21703289; 21922301; 21761132022; 21673074; 2016YFA0501700; 2019YFA090402; 2019YFA0905201; 18ZR1412600; 2632019FY01; 20H02701
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Computational chemistry; Quantum chemistry
Citation Formats
Liu, Jinfeng, Yang, Jinrong, Zeng, Xiao Cheng, Xantheas, Sotiris S., Yagi, Kiyoshi, and He, Xiao. Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21. United States: N. p., 2021.
Web. doi:10.1038/s41467-021-26284-x.
Liu, Jinfeng, Yang, Jinrong, Zeng, Xiao Cheng, Xantheas, Sotiris S., Yagi, Kiyoshi, & He, Xiao. Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21. United States. https://doi.org/10.1038/s41467-021-26284-x
Liu, Jinfeng, Yang, Jinrong, Zeng, Xiao Cheng, Xantheas, Sotiris S., Yagi, Kiyoshi, and He, Xiao. Fri .
"Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21". United States. https://doi.org/10.1038/s41467-021-26284-x. https://www.osti.gov/servlets/purl/1830221.
@article{osti_1830221,
title = {Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21},
author = {Liu, Jinfeng and Yang, Jinrong and Zeng, Xiao Cheng and Xantheas, Sotiris S. and Yagi, Kiyoshi and He, Xiao},
abstractNote = {The spectroscopic features of protonated water species in dilute acid solutions have been long sought after for understanding the microscopic behavior of the proton in water with gas-phase water clusters H+(H2O)n extensively studied as bottom-up model systems. We present a new protocol for the calculation of the infrared (IR) spectra of complex systems, which combines the fragment-based Coupled Cluster method and anharmonic vibrational quasi-degenerate perturbation theory, and demonstrate its accuracy towards the complete and accurate assignment of the IR spectrum of the H+(H2O)21 cluster. The site-specific IR spectral signatures reveal two distinct structures for the internal and surface four-coordinated water molecules, which are ice-like and liquid-like, respectively. The effect of inter-molecular interaction between water molecules is addressed, and the vibrational resonance is found between the O-H stretching fundamental and the bending overtone of the nearest neighboring water molecule. The revelation of the spectral signature of the excess proton offers deeper insight into the nature of charge accommodation in the extended hydrogen-bonding network underpinning this aqueous cluster.},
doi = {10.1038/s41467-021-26284-x},
journal = {Nature Communications},
number = 1,
volume = 12,
place = {United States},
year = {2021},
month = {10}
}
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