Anharmonic densities of states: A general dynamics-based solution

Jellinek, Julius; Aleinikava, Darya

doi:10.1063/1.4951695

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

Journal Article · Thu Jun 02 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4951695· OSTI ID:1344547

Jellinek, Julius ^[1]; Aleinikava, Darya ^[2]

Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Benedictine Univ., Lisle, IL (United States)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1344547

Alternate ID(s):: OSTI ID: 1421164

Journal Information:: Journal of Chemical Physics, Vol. 144, Issue 21; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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