skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on February 15, 2020

Title: Multifaceted Water Dynamics in Spherical Nanocages

Abstract

We present here a new method to study position-dependent, anisotropic diffusion tensors inside spherically confined systems—a geometry that is common to many chemical nanoreactors. We use this method to elucidate the surprisingly rich solvent dynamics of confined water. The spatial variation of the strongly anisotropic diffusion predicted by the model agrees with the results of explicit molecular dynamics simulations. The same approach can be directly transferred to the transport of solutes to and from reaction sites located at nanoreactor interfaces. We complement our study by a detailed analysis of water hydrogen bond kinetics, which is intimately coupled to diffusion. Despite the inhomogeneity in structure and translational dynamics inside our nanocages, a single set of well-defined rate constants is sufficient to accurately describe the kinetics of hydrogen bond breaking and formation. We find that once system size effects have been eliminated, the residence times of water molecules inside the coordination shell of a hydrogen bond partner are well correlated to average diffusion constants obtained from the procedure above.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [2]
  1. Univ. of California, Irvine, CA (United States). Dept. of Chemistry
  2. Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Chemistry
  3. Univ. of Bonn (Germany). Mulliken Center for Theoretical Chemistry
  4. Max Planck Inst. of Biophysics, Frankfurt (Germany)
Publication Date:
Research Org.:
Virginia Commonwealth Univ., Richmond, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1525959
Grant/Contract Number:  
SC0004406; AC02-05CH11231; CHE-1800120; OCI-1053575
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 10; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

von Domaros, Michael, Bratko, Dusan, Kirchner, Barbara, Hummer, Gerhard, and Luzar, Alenka. Multifaceted Water Dynamics in Spherical Nanocages. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.8b11567.
von Domaros, Michael, Bratko, Dusan, Kirchner, Barbara, Hummer, Gerhard, & Luzar, Alenka. Multifaceted Water Dynamics in Spherical Nanocages. United States. doi:10.1021/acs.jpcc.8b11567.
von Domaros, Michael, Bratko, Dusan, Kirchner, Barbara, Hummer, Gerhard, and Luzar, Alenka. Fri . "Multifaceted Water Dynamics in Spherical Nanocages". United States. doi:10.1021/acs.jpcc.8b11567.
@article{osti_1525959,
title = {Multifaceted Water Dynamics in Spherical Nanocages},
author = {von Domaros, Michael and Bratko, Dusan and Kirchner, Barbara and Hummer, Gerhard and Luzar, Alenka},
abstractNote = {We present here a new method to study position-dependent, anisotropic diffusion tensors inside spherically confined systems—a geometry that is common to many chemical nanoreactors. We use this method to elucidate the surprisingly rich solvent dynamics of confined water. The spatial variation of the strongly anisotropic diffusion predicted by the model agrees with the results of explicit molecular dynamics simulations. The same approach can be directly transferred to the transport of solutes to and from reaction sites located at nanoreactor interfaces. We complement our study by a detailed analysis of water hydrogen bond kinetics, which is intimately coupled to diffusion. Despite the inhomogeneity in structure and translational dynamics inside our nanocages, a single set of well-defined rate constants is sufficient to accurately describe the kinetics of hydrogen bond breaking and formation. We find that once system size effects have been eliminated, the residence times of water molecules inside the coordination shell of a hydrogen bond partner are well correlated to average diffusion constants obtained from the procedure above.},
doi = {10.1021/acs.jpcc.8b11567},
journal = {Journal of Physical Chemistry. C},
number = 10,
volume = 123,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on February 15, 2020
Publisher's Version of Record

Save / Share: