Comment to “Dynamics of supercooled confined water measured by deep inelastic neutron scattering”

We comment on the findings of “Dynamics of supercooled confined water measured by deep inelastic neutron scattering”, by V. De Michele, G. Romanelli, and A. Cupane [Front. Phys. 13, 138205 (2018)]. We show that the current sensitivity of the deep inelastic neutron scattering (DINS) method, cannot detect with confidence small differences in the proton kinetic energy, Ke(H), involved in a liquid-liquid transition in supercooled water confined in nanoporous silica. We also critisize the calculation of Ke(H) carried out in Front. Phys. 13, 138205 (2018).     

Dynamics of supercooled confined water measured by deep inelastic neutron scattering

In this paper, we present the results of deep inelastic neutron scattering (DINS) measurements on supercooled water confined within the pores (average pore diameter ~ 20 Å) of a disordered hydrophilic silica matrix obtained through hydrolysis and polycondensation of the alkoxide precursor Tetra-Methyl-Ortho-Silicate via the sol-gel method. Experiments were performed at two temperatures (250 K and 210 K, i.e., before and after the putative liquid–liquid transition of supercooled confined water) on a “wet” sample with hydration h ~ 40% w/w, which is high enough to have water-filled pores but low enough to avoid water crystallization. A virtually “dry” sample at h ~ 7% was also investigated to measure the contribution of the silica matrix to the neutron scattering signal. As is well known, DINS measurements allow the determination of the mean kinetic energy and the momentum distribution of the hydrogen atoms in the system and therefore, allow researchers to probe the local structure of supercooled confined water. The main result obtained is that at 210 K the hydrogen mean kinetic energy is equal or even slightly higher than at 250 K. This is at odds with the predictions of a semiempirical harmonic model recently proposed to describe the temperature dependence of the kinetic energy of hydrogen in water. This is a new and very interesting result, which suggests that at 210 K, the water hydrogens experience a stiffer intermolecular potential than at 250 K. This is in agreement with the liquid–liquid transition hypothesis.     

Lattice dynamics of Nb3Sn at 300 K

The phonon dispersion curves have been calculated from a microscopic model for Nb₃Sn at 300 K and are in good agreement with the available inelastic neutron scattering data. The calculated phonon density of states exhibits the essential features of the experimental results obtained by incoherent inelastic neutron scattering.     

Deep inelastic electron scattering and the rising σ(v)/σ(v) ratio

The rising $\text{σ(}\text{v}\text{)/σ(v)}$ ratio is quantitavely predicted from deep inelastic electron scattering, in particular from the scaling violations observed for the difference of the proton and neutron structure functions. The parametrization of the deviations from scaling is based on a simple two-component picture of deep inelastic scattering.     

Simultaneous measurement of lithium and fluorine momentum in (7)LiF

We present momentum widths and mean kinetic energies of lithium and fluorine in (7)LiF, as determined simultaneously from deep inelastic neutron scattering (DINS) measurements. Experimental data across a temperature range from 4 to 300?K are presented, and these results compared to those calculated using a quasi-harmonic density-functional approach. In all cases, measured momentum widths are seen to be within approximately 5% of those calculated, despite the very low scattering cross sections of both (7)Li and (19)F. This is the first determination and comparison with theory of such simultaneous measurements for nuclei of mass >?4?amu, and demonstrates the implementation of the DINS method in its current form as a mass-selective neutron spectroscopy.     

NEUTRON SCATTERING AND LATTICE DYNAMICAL STUDIES OF THE HIGH-PRESSURE PHASE ICE (I)

Lattice dynamical calculations of ice VIII have been carried out by using a slightly modified set of force constants obtained recently for ice Ih (Li J C and Ross D K 1993 Nature 365 327). A weak interaction was introduced between the two interpenetrated sublattices in the ice VIII structure. The calculated results for H₂O and D₂O ice VIII are in reasonable agreement with the measured inelastic neutron scattering spectra. The eigenvectors of phonon modes in the range of translational and librational bands have been studied in order to understand the properties of the vibrational modes. It is found that the third peak at 26.7meV in the translation results from weak hydrogen bond interactions, and the first peak (14.7meV) is much higher than it is in ice Ih (～7.1meV), which is partially due to the interactions between the two sublattices.     

Extraction of single-particle mean kinetic energy from macroscopic thermodynamic data

We have devised a simple and practical method for the extraction of single-particle mean kinetic energy from the Helmholtz free energy, when this quantity is known for a pair of isotopes of the element under investigation. This approach is originated from a property of the mass derivative of the Helmholtz free energy, but makes use of a mass incremental ratio evaluated for the aforementioned isotopes. The transformation from mass incremental ratio to mass derivative is done using a self-consistent method based on two approximations, the latter of which is quite surprising and has been thoroughly tested. Practical calculations on solid and liquid H₂ and D₂, where the center-of-mass mean kinetic energy is known from reliable quantum simulation techniques, are accomplished, obtaining a remarkable agreement, in spite of a slight overestimate for the calculated data set over the simulated one. The last part of the study is devoted to mixed systems, like water and ice, where thermodynamic data are abundant and proton mean kinetic energy has been measured via deep inelastic neutron scattering. Here results are less accurate than earlier, with an overestimate of about 9-10%, and, in addition, no substantial variation going from ice to liquid water. Further investigations on the H₂O/D₂O system are suggested.     

Vibrational spectra of high- and low-density amorphous ice,ice Ic,and ice Ih by neutron scattering

Abstract

The vibrational spectra of high- and low-density amorphous ice made ice Ic and Ice Ih have been obtained at 15 K using inelastic incoherent neutron scattering     

Dynamics of hydrogen-bonded water networks under high pressure: Neutron scattering and computer simulation

Abstract

Molecular dynamics simulation of proton-ordered high pressure ice modifications II and IX was performed. Dynamics of both isotope varieties, H₂O and D₂O, was simulated. Rectangular simulation box of ice II contained 576 and that of ice IX 768 molecules. The average kinetic energy corresponded to 82 and 201 K for ice II and to 87 and 203 K for ice IX. One-phonon densities of states were calculated via Fourier transformation of velocity autocorrelation functions and compared with those found experimentally from inelastic incoherent neutron scattering. This characteristic was calculated for all the molecules, as well as for the molecules of a particular crystallographic type. Both simulated ice modifications contain molecules of two different structural types. Dynamic characteristics of molecules of different types are slightly different. Splitting of the librational peak at about 60–70meV observed in the ice II experimental spectrum is mainly due to such difference. In the case of ice II simulated spectra reproduce experimental ones quite reasonably in the whole range of energies, while in the case of ice IX agreement with the experiment is worse.     

Anomalous behavior of proton zero point motion in water confined in carbon nanotubes

The momentum distribution of the protons in ice Ih, ice VI, high density amorphous ice, and water in carbon nanotubes has been measured using deep inelastic neutron scattering. We find that at 5 K the kinetic energy of the protons is 35 meV less than that in ice Ih at the same temperature, and the high momentum tail of the distribution, characteristic of the molecular covalent bond, is not present. We observe a phase transition between 230 and 268 K to a phase that does resemble ice Ih. Although there is yet no model for water that explains the low temperature momentum distribution, our data reveal that the protons in the hydrogen bonds are coherently delocalized and that the low temperature phase is a qualitatively new phase of ice.     

Quadrupole moments and nucleon excitation strengths in even-A Sm isotopes

We present a coherent coupled-channel analysis of 7 MeV neutron and 16 MeV proton elastic and inelastic scattering from ^{148, 152, 154}Sm. The optical potential and nuclear deformation parameters are determined so as to fit not only these elastic and inelastic scattering data but also the low-energy neutron scattering properties and the total cross sections over a wide energy range. This analysis provides evidence of the same excitation strengths for both projectiles in the case of ^{152, 154}Sm, and of a smaller excitation strength for the proton than for the neutron in case of ¹⁴⁸Sm. Moreover the quadrupole moments of these deformed optical potentials are in good agreement with those extracted from Coulomb excitation measurements and from nuclear matter distribution calculations.     

Search for anomalous effects in H2O/D2O mixtures by neutron total cross section measurements

We investigate anomalies ascribed to quantum entanglement phenomena recently reported in deep inelastc neutron scattering (DINS) measurements by an independent neutron technique on H(2)O/D(2)O mixtures. We performed transmission experiments to study several liquid H(2)O/D(2)O mixtures at room temperature in the epithermal energy range. We obtain the total cross sections of the mixtures, which are in agreement with the expected results according to the tabulated values within a 0.3% relative error. We observe no anomalies and stress the limitations of the validity of the data-processing procedures employed in the DINS experiments where the anomalies were reported.     

Nucleon scattering analysis from90,92,594Zr and isospin decomposition of transition matrix elements for low-lying collective transitions

Simultaneous analysis of neutron and proton inelastic scattering to low-lying collective states in^{90, 92, 94}Zr are used to derive an isospin decomposition of the corresponding transition matrix elements. The deduced (M _n/M_p) ratios for the strongest transitions are in sharp disagreement with values derived from Coulomb-nuclear interference observed in 35.4 MeV inelastic α-scattering from even Zr isotopes.     

Some properties of the phonon spectra of transition metal disilicides VSi2, NbSi2, and TaSi2

The phonon spectra of metallic disilicides VSi₂, NbSi₂, and TaSi₂ have been studied in detail by inelastic neutron scattering at 300 K and specific heat measurements between 10 K and 250 K. The specific heat calculated from the generalised phonon density of states extracted from neutron measurements is in good agreement with the measured lattice contribution to the specific heat. The properties of the phonon spectra are discussed in relation with other data reported for these isostructural and isoelectronic disilicides.     

Phonon density of states of V3Si

The phonon density of states of V₃Si at 300°K has been calculated from a microscopic model. It exhibits three pronounced peaks, in qualitative agreement with experimental results of Schweiss obtained from inelastic neutron scattering. By reducing the effective charges of both ions the agreement can be improved, but at the expense of agreement for the mode softening.     

Lattice dynamics and inelastic neutron scattering experiments on andalusite,Al2SiO5

We report coherent inelastic neutron scattering measurements of the phonon dispersion relations and lattice dynamics shell model calculations of several microscopic and macroscopic properties of andalusite, Al₂SiO₅. Andalusite has an orthorhombic structure with 32 atoms/unit cell. The inelastic neutron scattering measurements (up to energy transfers of 45 meV) were carried out using the triple axis spectrometer at Dhruva reactor, India using a single crystal of andalusite and the phonon dispersion relations along the [100] direction have been measured. The shell model calculations have been used to compute the crystal structure, elastic constants, phonon frequencies, dispersion relations, density of states and the specific heat. The calculated results are in good agreement with available experimental data. The computed one-phonon neutron scattering structure factors based on the shell model have been very useful in the planning and analysis of the inelastic neutron scattering experiments.     

Spin waves in Pd3Fe

The spin wave dispersion relation in ordered Pd₃Fe has been measured at 296°K by neutron inelastic scattering techniques. The results are compared with various models for the spin wave spectrum.     

Unravelling low lying phonons and vibrations of carbon nanostructures: The contribution of inelastic and quasi-elastic neutron scattering

We illustrate the contribution of inelastic neutron scattering to the understanding of the vibrations and lattice excitations of fullerenes and carbon nanotubes, through some significant experimental results. Particular emphasis is placed on the study of intra and inter-molecular modes of fullerene C₆₀, as well as on the order/disorder transition characteristic of these molecules. In addition, a significant part of this article is dedicated to various intercalation compounds of fullerenes and carbon nanotubes, such as the co-crystal ??fullerene-cubane?? consisting of an arrangement of molecules of spherical and cubic shapes, or the compound called ??peapods??, in which fullerene C₆₀ are inserted inside carbon nanotubes.     

Long-wavelength magnetic excitations in the Zn0.55Mn0.45Fe2O4 ferrite

The small-angle neutron scattering energy spectra of the Zn_0.55Mn_0.45Fe₂O₄ ferrite are analyzed at different temperatures (both below and above T _C ? 390 K) and scattering angles. The thermal expansion coefficient α(T) is measured in the temperature range 80–600 K. It is revealed that inelastic neutron scattering is governed not only by spin waves of the Holstein-Primakoff type but also by the substantial contribution of additional long-wavelength magnetic excitations. The physical nature of these low-energy magnetic excitations is discussed.     

Study of the glass transition order parameter in amorphous polybutadiene by incoherent neutron scattering

The temperature dependent elastic incoherent scattering from a glass forming polybutadiene was studied using high resolution neutron spectroscopy. This elastic scattering measures directly the non-ergodicity order parameter of the glass transition. We observed an anomalous decrease of this scattering setting in around 30 K below the thermodynamic glass transition,T _g , the temperature dependence of which is in agreement with the square root ofT prediction of the mode coupling approach. The critical temperature of 220 K lies about 30 K aboveT _g . The missing elastic intensity reappears as inelastic scattering in the 1 meV range. Within the eV resolution of the backscattering spectrometer no quasielastic scattering can be detected up to 20 K aboveT _g . The observed inelastic scattering may be interpreted as resulting from a continous shift of the density of states towards low frequencies as a consequence of a general softening of the structure.