Anharmonic densities of states: A general dynamicsbased 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, timedependent. 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:

 Argonne National Lab. (ANL), Argonne, IL (United States)
 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) (SC22). Chemical Sciences, Geosciences & Biosciences Division
 OSTI Identifier:
 1344547
 Alternate Identifier(s):
 OSTI ID: 1421164
 Grant/Contract Number:
 AC0206CH11357
 Resource Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 144; Journal Issue: 21; Journal ID: ISSN 00219606
 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 dynamicsbased solution. United States: N. p., 2016.
Web. doi:10.1063/1.4951695.
Jellinek, Julius, & Aleinikava, Darya. Anharmonic densities of states: A general dynamicsbased solution. United States. doi:10.1063/1.4951695.
Jellinek, Julius, and Aleinikava, Darya. Thu .
"Anharmonic densities of states: A general dynamicsbased 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 dynamicsbased 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, timedependent. 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}
}
Web of Science
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