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Title: Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations

Abstract

The aqueous proton is a common and long-studied species in chemistry, yet there is currently intense interest devoted to understanding its hydration structure and transport dynamics. Typically described in terms of two limiting structures observed in gas-phase clusters, the Zundel H5O2+ and Eigen H9O4+ ions, the aqueous structure is less clear due to the heterogeneity of hydrogen bonding environments and room-temperature structural fluctuations in water. The linear infrared (IR) spectrum, which reports on structural configurations, is challenging to interpret because it appears as a continuum of absorption, and the underlying vibrational modes are strongly anharmonically coupled to each other. Recent two-dimensional IR (2D IR) experiments presented strong evidence for asymmetric Zundel-like motifs in solution, but true structure–spectrum correlations are missing and complicated by the anharmonicity of the system. In this study, we employ high-level vibrational self-consistent field/virtual state configuration interaction calculations to demonstrate that the 2D IR spectrum reports on a broad distribution of geometric configurations of the aqueous proton. We find that the diagonal 2D IR spectrum around 1200 cm–1 is dominated by the proton stretch vibrations of Zundel-like and intermediate geometries, broadened by the heterogeneity of aqueous configurations. There is a wide distribution of multidimensional potential shapes formore » the proton stretching vibration with varying degrees of potential asymmetry and confinement. In conclusion, we find specific cross peak patterns due to aqueous Zundel-like species. These studies provide clarity on highly debated spectral assignments and stringent spectroscopic benchmarks for future simulations.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Chicago, IL (United States)
  2. Emory Univ., Atlanta, GA (United States); Yale Univ., New Haven, CT (United States)
  3. Emory Univ., Atlanta, GA (United States)
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1761055
Alternate Identifier(s):
OSTI ID: 1664558
Grant/Contract Number:  
SC0014305; CHE-1463552
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 153; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Probability theory; quantum state; chemical bonding; anharmonicity; potential energy surfaces; infrared spectroscopy; acids; two-dimensional optical spectoscopy

Citation Formats

Carpenter, William B., Yu, Qi, Hack, John H., Dereka, Bogdan, Bowman, Joel M., and Tokmakoff, Andrei. Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations. United States: N. p., 2020. Web. doi:10.1063/5.0020279.
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Carpenter, William B., Yu, Qi, Hack, John H., Dereka, Bogdan, Bowman, Joel M., & Tokmakoff, Andrei. Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations. United States. https://doi.org/10.1063/5.0020279
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Carpenter, William B., Yu, Qi, Hack, John H., Dereka, Bogdan, Bowman, Joel M., and Tokmakoff, Andrei. Wed . "Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations". United States. https://doi.org/10.1063/5.0020279. https://www.osti.gov/servlets/purl/1761055.
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@article{osti_1761055,
title = {Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations},
author = {Carpenter, William B. and Yu, Qi and Hack, John H. and Dereka, Bogdan and Bowman, Joel M. and Tokmakoff, Andrei},
abstractNote = {The aqueous proton is a common and long-studied species in chemistry, yet there is currently intense interest devoted to understanding its hydration structure and transport dynamics. Typically described in terms of two limiting structures observed in gas-phase clusters, the Zundel H5O2+ and Eigen H9O4+ ions, the aqueous structure is less clear due to the heterogeneity of hydrogen bonding environments and room-temperature structural fluctuations in water. The linear infrared (IR) spectrum, which reports on structural configurations, is challenging to interpret because it appears as a continuum of absorption, and the underlying vibrational modes are strongly anharmonically coupled to each other. Recent two-dimensional IR (2D IR) experiments presented strong evidence for asymmetric Zundel-like motifs in solution, but true structure–spectrum correlations are missing and complicated by the anharmonicity of the system. In this study, we employ high-level vibrational self-consistent field/virtual state configuration interaction calculations to demonstrate that the 2D IR spectrum reports on a broad distribution of geometric configurations of the aqueous proton. We find that the diagonal 2D IR spectrum around 1200 cm–1 is dominated by the proton stretch vibrations of Zundel-like and intermediate geometries, broadened by the heterogeneity of aqueous configurations. There is a wide distribution of multidimensional potential shapes for the proton stretching vibration with varying degrees of potential asymmetry and confinement. In conclusion, we find specific cross peak patterns due to aqueous Zundel-like species. These studies provide clarity on highly debated spectral assignments and stringent spectroscopic benchmarks for future simulations.},
doi = {10.1063/5.0020279},
journal = {Journal of Chemical Physics},
number = 12,
volume = 153,
place = {United States},
year = {Wed Sep 23 00:00:00 EDT 2020},
month = {Wed Sep 23 00:00:00 EDT 2020}
}
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