arXiv subjects

V. G. Artemov

Publications and source records attributed to V. G. Artemov.

6 recordsLinked to original sources

arXiv2020

Non-rotational mechanism of polarization in alcohols

Chemical polarity governs various mechanical, chemical and thermodynamic properties of dielectrics. Polar liquids have been amply studied, yet the basic mechanisms underpinning their dielectric properties remain not fully understood, as standard models following Debye's phenomenological approach do not account for quantum effects and cannot aptly reproduce the full dc-up-to-THz spectral range. Here, using the illustrative case of monohydric alcohols, we show that deep tunneling and the consequent intermolecular separation of excess protons and "proton-holes" in the polar liquids govern their static and dynamic dielectric properties on the same footing. We performed systematic ultrabroadband (0-10 THz) spectroscopy experiments with monohydric alcohols of different (0.4-1.6 nm) molecular lengths, and show that the finite lifetime of molecular species, and the proton-hole correlation length are the two principle parameters responsible for the dielectric response of all the studied alcohols across the entire frequency range. Our results demonstrate that a quantum non-rotational intermolecular mechanism drives the polarization in alcohols while the rotational mechanism of molecular polarization plays a secondary role, manifesting itself in the sub-terahertz region only.

physics.chem-ph↗

arXiv2020

Revealing excess protons in the infrared spectrum of liquid water

The most common species in liquid water, next to neutral H$_2$O molecules, are the H$_3$O$^+$ and OH$^-$ ions. In a dynamic picture, their exact concentrations depend on the time scale at which these are probed. Here, using a spectral-weight analysis, we experimentally resolve the fingerprints of the elusive fluctuations-born short-living H$_3$O$^+$, DH$_2$O$^+$, HD$_2$O$^+$, and D$_3$O$^+$ ions in the IR spectra of light (H$_2$O), heavy (D$_2$O), and semi-heavy (HDO) water. We find that short-living ions, with concentrations reaching $\sim 2\%$ of the content of water molecules, coexist with long-living pH-active ions on the picosecond timescale, thus making liquid water an effective ionic liquid in femtochemistry.

cond-mat.mtrl-sci↗

arXiv2016

Diffusion-Oscillatory Dynamics in Liquid Water on Data of Dielectric Spectroscopy

When analyzing the broadband absorption spectrum of liquid water (10^10 - 10^13 Hz), we find its relaxation-resonance features to be an indication of Frenkel's translation-oscillation motion of particles, which is fundamentally inherent to liquids. We have developed a model of water structure, of which the dynamics is due to diffusion of particles, neutral H2O molecules and H3O+ and OH- ions - with their periodic localizations and mutual transformations. This model establishes for the first time a link between the dc conductivity, the Debye and the high frequency sub-Debye relaxations and the infrared absorption peak at 180 cm-1. The model reveals the characteristic times of the relaxations, 50 ps and 3 ps, as the lifetimes of water molecules and water ions, respectively. The model sheds light on the anomalous mobility of a proton and casts doubt on the long lifetime of a water molecule, 10 hours, commonly associated with autoionization.

cond-mat.soft↗

arXiv2015

Autoionization of water: does it really occur?

The ionization constant of water Kw is currently determined on the proton conductivity sigma1 which is measured at frequencies lower than 10^7 Hz. Here, we develop the idea that the high frequency conductivity sigma2 (~10^11 Hz), rather than sigma1 represents a net proton dynamics in water, to evaluate the actual concentration c of H3O+ and OH- ions from sigma2. We find c to be not dependent on temperature to conclude that i) water electrodynamics is due to a proton exchange between H3O+ (or OH-) ions and neutral H2O molecules rather than spontaneous ionization of H2O molecules, ii) the common Kw (or pH) reflects the thermoactivation of the H3O+ and OH- ions from the potential of their interaction, iii) the lifetime of a target water molecule does not exceed parts of nanosecond.

physics.chem-ph↗

arXiv2013

Water and Ice Dielectric Spectra Scaling at 0 °C

Dielectric spectra (10^4-10^11 Hz) of water and ice at 0 °C are considered in terms of proton conductivity and compared to each other. In this picture, the Debye relaxations, centered at 1/τ_W ~ 20 GHz (in water) and 1/τ_I ~ 5 kHz (in ice), are seen as manifestations of diffusion of separated charges in the form of H3O+ and OH- ions. The charge separation results from the self-dissociation of H2O molecules, and is accompanied by recombination in order to maintain the equilibrium concentration, N. The charge recombination is a diffusion-controlled process with characteristic lifetimes of τ_W and τ_I, for water and ice respectively. The static permittivity, ε(0), is solely determined by N. Both, N and ε(0), are roughly constant at the water-ice phase transition, and both increase, due to a slowing down of the diffusion rate, as the temperature is lowered. The transformation of the broadband dielectric spectra at 0 °C with the drastic change from τ_W to τ_I is mainly due to an abrupt (by 0.4 eV) change of the activation energy of the charge diffusion.

cond-mat.soft↗

arXiv2013

Proton Electrodynamics in Liquid Water

The dielectric spectrum of liquid water, $10^{4} - 10^{11}$ Hz, is interpreted in terms of diffusion of charges, formed as a result of self-ionization of H$_{2}$O molecules. This approach explains the Debye relaxation and the dc conductivity as two manifestations of this diffusion. The Debye relaxation is due to the charge diffusion with a fast recombination rate, $1/τ_{2}$, while the dc conductivity is a manifestation of the diffusion with a much slower recombination rate, $1/τ_{1}$. Applying a simple model based on Brownian-like diffusion, we find $τ_{2} \simeq 10^{-11}$ s and $τ_{1} \simeq 10^{-6}$ s, and the concentrations of the charge carriers, involved in each of the two processes, $N_{2} \simeq 5 \times 10^{26}$ m$^{-3}$ and $N_{1} \simeq 10^{14}$ m$^{-3}$. Further, we relate $N_{2}$ and $N_{1}$ to the total concentration of H$_{3}$O$^{+}$--OH$^{-}$ pairs and to the pH index, respectively, and find the lifetime of a single water molecule, $τ_{0} \simeq 10^{-9}$ s. Finally, we show that the high permittivity of water results mostly from flickering of separated charges, rather than from reorientations of intact molecular dipoles.

physics.chem-ph↗