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Title: Anharmonic densities of states: A general dynamics-based solution

Abstract

Density of states is a fundamental physical characteristic that lies at the foundation of statistical mechanics and theoretical constructs that derive from them (e.g., kinetic rate theories, phase diagrams, and others). Even though most real physical systems are anharmonic, the vibrational density of states is customarily treated within the harmonic approximation, or with some partial, often limited, account for anharmonicity. The reason for this is that the problem of anharmonic densities of states stubbornly resisted a general and exact, yet convenient and straightforward in applications, solution. Here, in this work, we formulate such a solution within both classical and quantum mechanics. It is based on actual dynamical behavior of systems as a function of energy and as observed, or monitored, on a chosen time scale, short or long. As a consequence, the resulting anharmonic densities of states are fully dynamically informed and, in general, time-dependent. As such, they lay the ground for formulation of new statistical mechanical frameworks that incorporate time and are ergodic, by construction, with respect to actual dynamical behavior of systems.

Authors:
 [1];  [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Benedictine Univ., Lisle, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1344547
Alternate Identifier(s):
OSTI ID: 1421164
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 21; 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

Citation Formats

Jellinek, Julius, and Aleinikava, Darya. Anharmonic densities of states: A general dynamics-based solution. United States: N. p., 2016. Web. doi:10.1063/1.4951695.
Jellinek, Julius, & Aleinikava, Darya. Anharmonic densities of states: A general dynamics-based solution. United States. doi:10.1063/1.4951695.
Jellinek, Julius, and Aleinikava, Darya. Thu . "Anharmonic densities of states: A general dynamics-based solution". United States. doi:10.1063/1.4951695. https://www.osti.gov/servlets/purl/1344547.
@article{osti_1344547,
title = {Anharmonic densities of states: A general dynamics-based solution},
author = {Jellinek, Julius and Aleinikava, Darya},
abstractNote = {Density of states is a fundamental physical characteristic that lies at the foundation of statistical mechanics and theoretical constructs that derive from them (e.g., kinetic rate theories, phase diagrams, and others). Even though most real physical systems are anharmonic, the vibrational density of states is customarily treated within the harmonic approximation, or with some partial, often limited, account for anharmonicity. The reason for this is that the problem of anharmonic densities of states stubbornly resisted a general and exact, yet convenient and straightforward in applications, solution. Here, in this work, we formulate such a solution within both classical and quantum mechanics. It is based on actual dynamical behavior of systems as a function of energy and as observed, or monitored, on a chosen time scale, short or long. As a consequence, the resulting anharmonic densities of states are fully dynamically informed and, in general, time-dependent. As such, they lay the ground for formulation of new statistical mechanical frameworks that incorporate time and are ergodic, by construction, with respect to actual dynamical behavior of systems.},
doi = {10.1063/1.4951695},
journal = {Journal of Chemical Physics},
number = 21,
volume = 144,
place = {United States},
year = {2016},
month = {6}
}

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