Intramolecular structure and energetics in supercooled water down to 255 K

Lehmkühler, Felix; Forov, Yury; Büning, Thomas; Sahle, Christoph J.; Steinke, Ingo; Julius, Karin; Buslaps, T.; Tolan, Metin; Hakala, Mikko; Sternemann, Christian

doi:10.1039/c5cp07721d

Cited by 18 publications

(12 citation statements)

References 63 publications

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“…Soft X-ray oxygen 1s X-ray absorption spectroscopy (XAS), electron energy loss spectroscopy (EELS), and equivalent information from hard X-ray Raman scattering (XRS) for the oxygen 1s excitations have been used to characterize the various phases of water (11, 22–27). In these studies, integral or area normalization within the measured spectral range between 530 and 550 eV has typically been used, with the aim to fulfill the theoretical concept of the f-sum rule (28) present for an ideal—complete—spectral range with clearly discernible bound and continuum states.…”

Section: X-ray Absorption Spectramentioning

confidence: 99%

Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions

Niskanen

Fondell

Sahle

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

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The phase diagram of water harbors controversial views on underlying structural properties of its constituting molecular moieties, its fluctuating hydrogen-bonding network, as well as pair-correlation functions. In this work, long energy-range detection of the X-ray absorption allows us to unambiguously calibrate the spectra for water gas, liquid, and ice by the experimental atomic ionization cross-section. In liquid water, we extract the mean value of 1.74 ± 2.1% donated and accepted hydrogen bonds per molecule, pointing to a continuous-distribution model. In addition, resonant inelastic X-ray scattering with unprecedented energy resolution also supports continuous distribution of molecular neighborhoods within liquid water, as do X-ray emission spectra once the femtosecond scattering duration and proton dynamics in resonant X-ray–matter interaction are taken into account. Thus, X-ray spectra of liquid water in ambient conditions can be understood without a two-structure model, whereas the occurrence of nanoscale-length correlations within the continuous distribution remains open.

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Section: X-ray Absorption Spectramentioning

confidence: 99%

Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions

Niskanen

Fondell

Sahle

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

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“…33 In this work, we present a study of the influence of TMAO and urea on the structure of water using X-ray Raman scattering (XRS) spectroscopy at the oxygen K-edge of aqueous solutions of urea, TMAO, and mixtures of the two. XRS has been shown to be sensitive to the structure of water and its hydrogen bonding topology across the extensive phase diagram, [44][45][46][47][48][49][50] as well as in aqueous solutions. [51][52][53][54] The use of XRS, thus, allows us to gain element specific spectroscopic information about the systems under relevant thermodynamic conditions without, for example, isotopic substitutions.…”

Section: Introductionmentioning

confidence: 99%

Influence of TMAO and urea on the structure of water studied by inelastic X-ray scattering

Sahle

Schroer

Juurinen

et al. 2016

Phys. Chem. Chem. Phys.

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We present a study on the influence of the naturally occurring organic osmolytes tri-methylamine N-oxide (TMAO) and urea on the bulk structure of water using X-ray Raman scattering spectroscopy. Addition of TMAO is known to stabilize proteins in otherwise destabilizing aqueous urea solutions. The experimental X-ray Raman scattering spectra change systematically with increasing solute concentration revealing different effects on the structure of water due to the presence of the two osmolytes. Although these effects are distinct for both molecular species, they have mutually compensating influences on the spectra of the ternary water-TMAO-urea mixtures. This compensation effect seen in the spectra vanishes only at the highest studied ternary concentration of 4 M : 4 M (TMAO : urea). Our experiment shows that the hydrogen-bonding structure of water remains rather intact in the presence of the aforementioned osmolytes if both of them are present.

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“…[132][133][134]. Recent advances in X-ray spectroscopy [135][136][137][138] hold the potential of computing bond orientational order from scattering experiments, and could open a new era in the investigation of local structural information in disordered systems. The idea of studying crystallization under external fields by studying the effects of the field on the bond orientational order is also a new direction for future research, which has been considered for example in Ref.…”

Section: Translational Vs Orientational Order Curvesmentioning

confidence: 99%

Crystal nucleation as the ordering of multiple order parameters

Russo

Tanaka

2016

The Journal of Chemical Physics

105

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Nucleation is an activated process in which the system has to overcome a free energy barrier in order for a first-order phase transition between the metastable and the stable phases to take place. In the liquid-to-solid transition the process occurs between phases of different symmetry, and it is thus inherently a multi-dimensional process, in which all symmetries are broken at the transition. In this Focus Article, we consider some recent studies which highlight the multi-dimensional nature of the nucleation process. Even for a single-component system, the formation of solid crystals from the metastable melt involves fluctuations of two (or more) order parameters, often associated with the decoupling of positional and orientational symmetry breaking. In other words, we need at least two order parameters to describe the free-energy of a system including its liquid and crystalline states. This decoupling occurs naturally for asymmetric particles or directional interactions, focusing here on the case of water, but we will show that it also affects spherically symmetric interacting particles, such as the hard-sphere system. We will show how the treatment of nucleation as a multi-dimensional process has shed new light on the process of polymorph selection, on the effect of external fields on the nucleation process, and on glass-forming ability.

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Intramolecular structure and energetics in supercooled water down to 255 K

Cited by 18 publications

References 63 publications

Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions

Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions

Influence of TMAO and urea on the structure of water studied by inelastic X-ray scattering

Crystal nucleation as the ordering of multiple order parameters

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