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

Abstract

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:
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)
OSTI Identifier:
1306686
Grant/Contract Number:
667205; 2013-8823; AC02-06CH11357
Resource Type:
Journal Article: 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)
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

Citation Formats

Schlesinger, Daniel, Wikfeldt, K. Thor, Skinner, Lawrie B., Benmore, Chris J., Nilsson, Anders, and Pettersson, Lars G. M. The temperature dependence of intermediate range oxygen-oxygen correlations in liquid water. United States: N. p., 2016. Web. doi:10.1063/1.4961404.
Schlesinger, Daniel, Wikfeldt, K. Thor, Skinner, Lawrie B., Benmore, Chris J., Nilsson, Anders, & Pettersson, Lars G. M. The temperature dependence of intermediate range oxygen-oxygen correlations in liquid water. United States. doi:10.1063/1.4961404.
Schlesinger, Daniel, Wikfeldt, K. Thor, Skinner, Lawrie B., Benmore, Chris J., Nilsson, Anders, and Pettersson, Lars G. M. 2016. "The temperature dependence of intermediate range oxygen-oxygen correlations in liquid water". United States. doi:10.1063/1.4961404.
@article{osti_1306686,
title = {The temperature dependence of intermediate range oxygen-oxygen correlations in liquid water},
author = {Schlesinger, Daniel and Wikfeldt, K. Thor and Skinner, Lawrie B. and Benmore, Chris J. and Nilsson, Anders and Pettersson, Lars G. M.},
abstractNote = {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.},
doi = {10.1063/1.4961404},
journal = {Journal of Chemical Physics},
number = 8,
volume = 145,
place = {United States},
year = 2016,
month = 8
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4961404

Citation Metrics:
Cited by: 3works
Citation information provided by
Web of Science

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  • 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 amore » 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.« less
  • 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 collectivemore » 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.« less
  • Cited by 3
  • The NMR proton spin--lattice relaxation times T/sub 1/ and shear viscosities have been measured as functions of pressure in the temperature interval -15--10 degreeC. At low temperatures the low pressure boundary of the experiments is ice I, whereas ice V represents the high pressure extreme of our measurements. The initial compression at all temperatures covered in our study results in higher motional freedom of water molecules so that the pressure dependence exhibits a minimum in viscosity and a maximum in T/sub 1/. This is a consequence of significant distortion of the hydrogen bond network due to compression which also seemsmore » to weaken the hydrogen bonds. Further compression leads to restricted motional freedom due to increased packing of the molecules. This anomalous behavior of spin--lattice relaxation and shear viscosity with compression is more pronounced at lower temperatures since the hydrogen bond network is better developed at lower temperatures. In agreement with our earlier data covering the 10--90 degreeC temperature range, we find that compression under isothermal conditions distorts the random hydrogen bond network, leading to diminished coupling between the rotational and translational motions of water molecules. The data indicate that the Debye equation describes the relationship between the reorientational correlation time and shear viscosity at constant volume but is not applicable to describe the density effects on water reorientation. In general, pressure and temperature have parallel effects on many dynamic properties at temperatures below 40 degreeC and pressures below 2 kbar, whereas at higher temperatures and pressures their effects are just the opposite. Hard core repulsive interactions become more important than the directional interactions of hydrogen bonding at high compression. (AIP)« less
  • In a recent article by the Castner and Margulis groups [Faraday Discuss. 154, 133 (2012)], we described in detail the structure of the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)-amide ionic liquid as a function of temperature using X-ray scattering, and theoretical partitions of the computationally derived structure function. Interestingly, and as opposed to the case in most other ionic-liquids, the first sharp diffraction peak or prepeak appears to increase in intensity as temperature is increased. This phenomenon is counter intuitive as one would expect that intermediate range order fades as temperature increases. This Communication shows that a loss of hydrophobic tail organization at highermore » temperatures is counterbalanced by better organization of polar components giving rise to the increase in intensity of the prepeak.« less