A Phase Space Signature of Quantum Roaming in Chesnavich's Model

• URL: http://arxiv.org/abs/2605.30872v1
• Date: Fri, 29 May 2026 05:51:44 GMT
• Title: A Phase Space Signature of Quantum Roaming in Chesnavich's Model
• Abstract summary: Roaming reactions occur when a molecule enters a near-dissociation region, avoids immediate separation, and later forms products.<n>Can a single quantum resonance carry a recognizable signature of the classical roaming region?<n>We interpret this state as a phase-space-localized quantum analogue of classical roaming.
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• License: http://creativecommons.org/licenses/by/4.0/
• Abstract: Roaming reactions occur when a molecule enters a near-dissociation region, avoids immediate separation, and later forms products by a pathway not controlled by the conventional tight transition-state bottleneck. Classical studies have shown that roaming is best understood in phase space: inner and outer transition-state structures, together with their invariant manifolds, organize trapping, return, and dissociation. The corresponding quantum question is less settled. Can a single quantum resonance carry a recognizable signature of the classical roaming region? We address this question in Chesnavich's two-degree-of-freedom model for the ion--molecule reaction $\mathrm{CH}_4^+\rightarrow\mathrm{CH}_3^+ + \mathrm{H}$. Resonance states are computed with a complex absorbing potential and analyzed using diagnostics designed to mirror the classical phase-space picture: radial probability weights derived from the tight and outer transition-state structures, radial Husimi projections, angular-momentum channel weights, and coherent-state probes of the classical periodic orbits. One resonance is distinguished from the rest of the computed resonance ensemble. Its wavefunction is concentrated in the projected region between the inner and outer transition-state structures, its radial phase-space distribution is centered at intermediate radius with nearly zero radial momentum, and its angular structure is consistent with a standing rather than a directed rotating component. We interpret this state as a phase-space-localized quantum analogue of classical roaming. The result provides a controlled example in which quantum roaming is identified directly from a resonance wavefunction and its phase-space diagnostics, rather than only from product-state or scattering signatures.

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