Lossless and Lossy Characterization of the State of Perturbed Anharmonic Diatomics: An Information-Theoretic Compaction of Quantum Dynamics
A lossless, exact compaction of the time-evolved state of the quantum dynamical system of a perturbed anharmonic molecule is demonstrated using dynamical symmetries. The density matrix of the anharmonic molecule is a linear combination of these symmetries, and it remains so as a time-dependent perturbation is applied. Accurate, unitary-but-approximate, and thereby irreversible compaction is further shown using fewer symmetries, and the fidelity of this lossy compaction is quantified. Perturbations are typically linear in the operators of a Lie algebra. For a Hamiltonian that is also linear, one knows well how to reversibly compact the state of a dynamical system. However, anharmonic vibrations have a finite number of unequally spaced energy levels, and a good description of their spectra typically requires an algebraic-type Hamiltonian that is bilinear in the operators of a Lie algebra. For a bilinear Hamiltonian we show how a matrix-based approach allows us to compact both the populations and the coherences, either exactly reversibly or inexactly irreversibly, with fewer symmetries. A forced Morse oscillator is used as an explicit analytical and numerical example covering the entire range of dynamics from the sudden to the adiabatic limits.
Authors
- James Russell Hamilton (ORCID: https://orcid.org/0000-0002-4214-5561)
- Raphael D. Levine
Institutions
- Hebrew University of Jerusalem (IL)
- University of California System (US)
- St David's Medical Center (US)
Publication Details
- Journal
- Journal of Chemical Theory and Computation
- Published
- 2026-02-18
- DOI
- https://doi.org/10.1021/acs.jctc.6c00025
- Primary Topic
- Quantum Mechanics and Non-Hermitian Physics
- Type
- article
- Field-Weighted Citation Impact
- 0.00