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Title: The temperature dependence of intermediate range oxygen-oxygen correlations in liquid water

Here, we analyze the recent temperature dependent oxygen-oxygen pair-distribution functions from experimental high-precision x-ray diffraction data of bulk water by Skinner et al. [J. Chem. Phys. 141, 214507 (2014)] with particular focus on the intermediate range where small, but significant, correlations are found out to 17 Å. The second peak in the pair-distribution function at 4.5 Å is connected to tetrahedral coordination and was shown by Skinner et al. to change behavior with temperature below the temperature of minimum isothermal compressibility. Here we show that this is associated also with a peak growing at 11 Å which strongly indicates a collective character of fluctuations leading to the enhanced compressibility at lower temperatures. We note that the peak at ~13.2 Å exhibits a temperature dependence similar to that of the density with a maximum close to 277 K or 4 °C. We analyze simulations of the TIP4P/2005 water model in the same manner and find excellent agreement between simulations and experiment albeit with a temperature shift of ~20 K.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3] ;  [4] ;  [5] ; ORCiD logo [1]
  1. Stockholm Univ., Stockholm (Sweden)
  2. Stockholm Univ., Stockholm (Sweden); Univ. of Iceland, Reykjavik (Iceland)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Stanford Univ., Stanford, CA (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Stockholm Univ., Stockholm (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Grant/Contract Number:
667205; 2013-8823; AC02-06CH11357
Type:
Published Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
European Research Council (ERC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; liquid structure simulation; scattering measurements; experiment design; high pressure; hydrogen bonding
OSTI Identifier:
1306686
Alternate Identifier(s):
OSTI ID: 1312725; OSTI ID: 1389307