V-T theory for the Self-Intermediate Scattering Function in a Monatomic Liquid

Wallace, Duane C.; Chisolm, Eric D.; De Lorenzi-Venneri, Giulia

doi:10.1088/1361-648X/29/5/055101

Title: V-T theory for the Self-Intermediate Scattering Function in a Monatomic Liquid

Full Record
Other Related Research

Abstract

In V-T theory the atomic motion is harmonic vibrations in a liquid-specific potential energy valley, plus transits, which move the system rapidly among the multitude of such valleys. Here, in its first application to the self intermediate scattering function (SISF), V-T theory produced an accurate account of molecular dynamics (MD) data at all wave numbers q and time t. Recently, analysis of the mean square displacement (MSD) resolved a crossover behavior that was not observed in the SISF study. Our purpose here is to apply the more accurate MSD calibration to the SISF, and assess the results. We derive and discuss the theoretical equations for vibrational and transit contributions to the SISF. The time evolution is divided into three successive intervals: the vibrational interval when the vibrational contribution alone accurately accounts for the MD data; the crossover when the vibrational contribution saturates and the transit contribution becomes resolved; and the diffusive interval when the transit contribution alone accurately accounts for the MD data. Finally, the resulting theoretical error is extremely small at all q and t. V-T theory is compared to mode-coupling theories for the MSD and SISF, and to recent developments in Brownian motion experiments and theory.

Authors:

Wallace, Duane C. ^[1]; Chisolm, Eric D. ^[1]; De Lorenzi-Venneri, Giulia ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Publication Date:: Mon Dec 12 00:00:00 EST 2016

Research Org.:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1414129

Alternate Identifier(s):: OSTI ID: 1335200

Report Number(s):: LA-UR-16-26145
Journal ID: ISSN 0953-8984; TRN: US1800654

Grant/Contract Number:: AC52-06NA25396

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physics. Condensed Matter

Additional Journal Information:: Journal Volume: 29; Journal Issue: 5; Journal ID: ISSN 0953-8984

Publisher:: IOP Publishing

Country of Publication:: United States

Language:: English

Subject:: 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Liquid Theory; Liquid Dynamics; Time Correlation Functions; Liquid Structure; Diffusion, Atomic Motion

Citation Formats


                    Wallace, Duane C., Chisolm, Eric D., and De Lorenzi-Venneri, Giulia. V-T theory for the Self-Intermediate Scattering Function in a Monatomic Liquid.  United States: N. p., 2016. 
Web.  doi:10.1088/1361-648X/29/5/055101.

Copy to clipboard


                    Wallace, Duane C., Chisolm, Eric D., & De Lorenzi-Venneri, Giulia. V-T theory for the Self-Intermediate Scattering Function in a Monatomic Liquid.  United States.  https://doi.org/10.1088/1361-648X/29/5/055101

Copy to clipboard


                    Wallace, Duane C., Chisolm, Eric D., and De Lorenzi-Venneri, Giulia. Mon .  
"V-T theory for the Self-Intermediate Scattering Function in a Monatomic Liquid".  United States.  https://doi.org/10.1088/1361-648X/29/5/055101.  https://www.osti.gov/servlets/purl/1414129.

Copy to clipboard


                    
@article{osti_1414129,

  title        = {V-T theory for the Self-Intermediate Scattering Function in a Monatomic Liquid},

  author       = {Wallace, Duane C. and Chisolm, Eric D. and De Lorenzi-Venneri, Giulia},

  abstractNote = {In V-T theory the atomic motion is harmonic vibrations in a liquid-specific potential energy valley, plus transits, which move the system rapidly among the multitude of such valleys. Here, in its first application to the self intermediate scattering function (SISF), V-T theory produced an accurate account of molecular dynamics (MD) data at all wave numbers q and time t. Recently, analysis of the mean square displacement (MSD) resolved a crossover behavior that was not observed in the SISF study. Our purpose here is to apply the more accurate MSD calibration to the SISF, and assess the results. We derive and discuss the theoretical equations for vibrational and transit contributions to the SISF. The time evolution is divided into three successive intervals: the vibrational interval when the vibrational contribution alone accurately accounts for the MD data; the crossover when the vibrational contribution saturates and the transit contribution becomes resolved; and the diffusive interval when the transit contribution alone accurately accounts for the MD data. Finally, the resulting theoretical error is extremely small at all q and t. V-T theory is compared to mode-coupling theories for the MSD and SISF, and to recent developments in Brownian motion experiments and theory.},

  doi          = {10.1088/1361-648X/29/5/055101},

  journal      = {Journal of Physics. Condensed Matter},

  number       = 5,

  volume       = 29,

  place        = {United States},

  year         = {Mon Dec 12 00:00:00 EST 2016},

  month        = {Mon Dec 12 00:00:00 EST 2016}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1088/1361-648X/29/5/055101

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Atomic motion from the mean square displacement in a monatomic liquid

Journal Article Wallace, Duane C. ; De Lorenzi-Venneri, Giulia ; Chisolm, Eric D. - Journal of Physics. Condensed Matter

V-T theory is constructed in the many-body Hamiltonian formulation, and is being developed as a novel approach to liquid dynamics theory. In this theory the liquid atomic motion consists of two contributions, normal mode vibrations in a single representative potential energy valley, and transits, which carry the system across boundaries between valleys. The mean square displacement time correlation function (the MSD) is a direct measure of the atomic motion, and our goal is to determine if the V-T formalism can produce a physically sensible account of this motion. We employ molecular dynamics (MD) data for a system representing liquid Na,more »« less
Cited by 11
https://doi.org/10.1088/0953-8984/28/18/185101

Full Text Available
An improved model for the transit entropy of monatomic liquids

Journal Article Wallace, Duane C ; Chisolm, Eric D ; Bock, Nicolas - Physical Review E

In the original formulation of V-T theory for monatomic liquid dynamics, the transit contribution to entropy was taken to be a universal constant, calibrated to the constant-volume entropy of melting. This model suffers two deficiencies: (a) it does not account for experimental entropy differences of {+-}2% among elemental liquids, and (b) it implies a value of zero for the transit contribution to internal energy. The purpose of this paper is to correct these deficiencies. To this end, the V-T equation for entropy is fitted to an overall accuracy of {+-}0.1% to the available experimental high temperature entropy data for elementalmore »« less
https://doi.org/10.1103/PhysRevE.79.051201

Full Text Available
Potential energy surface of monatomic liquids

Journal Article Sjostrom, Travis ; De Lorenzi-Venneri, Giulia ; Wallace, Duane C. - Physical Review. B

In the last decade, significant progress has been made in the many-body Hamiltonian formulation of liquid dynamics theory. Earlier analysis of experimental data for a wide variety of elemental liquids had provided the reliable but qualitative description of the atomic motion: vibrations in a representative 3N -dimensional potential energy valley, plus transits, in which atoms cross the intersections between these valleys. Recent comparisons of first-principles theory with experiment for several elemental liquids at melt revealed a highly accurate and versatile theory. In the present work, we report on an extensive quench study of the entire condensed-matter structure-energy distribution for amore »« less
Cited by 5
https://doi.org/10.1103/physrevb.98.054201

Full Text Available
Vibrational theory for monatomic liquids

Journal Article Wallace, Duane C. ; Rudin, Sven Peter ; De Lorenzi-Venneri, Giulia ; ... - Physical Review B

The construction of the vibration-transit theory of liquid dynamics is being presented in three sequential research reports. The first is on the entire condensed-matter collection of N-atom potential energy valleys and identification of the random valleys as the liquid domain. The present (second) report defines the vibrational Hamiltonian and describes its application to statistical mechanics. The following is a brief list of the major topics treated here. The vibrational Hamiltonian is universal, in that its potential energy is a single 3N-dimensional harmonic valley. The anharmonic contribution is also treated. The Hamiltonian is calibrated from first-principles calculations of the structural potentialmore »« less
Cited by 6
https://doi.org/10.1103/PhysRevB.99.104204

Full Text Available
High Resolution studies of Tropolone in the So and S1 Electronic States: Isotope Driven Dynamics in the Zero-Point Energy Levels

Journal Article Keske, John C ; Lin, Wei ; Pringle, Wallace C ; ... - Journal of Chemical Physics

Rotationally resolved microwave (MW) and ultraviolet (UV) spectra of jet-cooled tropolone have been obtained in S0 and S1 electronic states using Fourier-transform microwave and UV laser/molecular beam spectrometers. In the ground electronic state, the MW spectra of all heavy atom isotopomers including one 18O and four 13C isotopomers were observed in natural abundance. The OD isotopomer was obtained from isotopically enriched samples. The two lowest tunneling states of each isotopomer except 18O have been assigned. For the asymmetric 13C structures, the magnitudes of tunneling-rotation interactions diminished with decreasing distance between the heavy atom and the tunneling proton. In the limitmore »« less
https://doi.org/10.1063/1.2165652

Similar Records