Erratum: “The inherent dynamics of a molecular liquid: Geodesic pathways through the potential energy landscape of a liquid of linear molecules” [J. Chem. Phys. 140, 174503 (2014)]

The geodesic (shortest) pathways through the potential energy landscape of a liquid can be thought of as defining what its dynamics would be if thermal noise were removed, revealing what we have called the "inherent dynamics" of the liquid. We show how these inherent paths can be located for a model liquid crystal former, showing, in the process, how the molecular mechanisms of translation and reorientation compare in the isotropic and nematic phases of these systems. These mechanisms turn out to favor the preservation of local orientational order even under macroscopically isotropic conditions (a finding consistent with the experimental observation of pseudonematic domains in these cases), but disfavor the maintenance of macroscopic orientational order, even in the nematic phase. While the most efficient nematic pathways that maintain nematic order are indeed shorter than those that do not, it is apparently difficult for the system to locate these paths, suggesting that molecular motion in liquid-crystal formers is dynamically frustrated, and reinforcing the sense that there are strong analogies between liquid crystals and supercooled liquids.

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The inherent dynamics of isotropic- and nematic-phase liquid crystals

Frechette

Stratt

2016

The Journal of Chemical Physics

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What is special about how roaming chemical reactions traverse their potential surfaces? Differences in geodesic paths between roaming and non-roaming events

Cofer-Shabica

Stratt

2017

The Journal of Chemical Physics

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With the notable exception of some illustrative two-degree-of-freedom models whose surprising classical dynamics has been worked out in detail, theories of roaming have largely bypassed the issue of when and why the counterintuitive phenomenon of roaming occurs. We propose that a useful way to begin to address these issues is to look for the geodesic (most efficient) pathways through the potential surfaces of candidate systems. Although roaming manifests itself in an unusual behavior at asymptotic geometries, we found in the case of formaldehyde dissociation that it was the pathways traversing the parts of the potential surface corresponding to highly vibrationally excited reactants that were the most revealing. An examination of the geodesics for roaming pathways in this region finds that they are much less tightly defined than the geodesics in that same region that lead directly to dissociation (whether into closed-shell products or into radical products). Thus, the broader set of options available to the roaming channel gives it an entropic advantage over more conventional reaction channels. These observations suggest that what leads to roaming in other systems may be less the presence of a localized "roaming transition state," than the existence of an entire region of the potential surface conducive to multiple equivalent pathways.

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Erratum: “The inherent dynamics of a molecular liquid: Geodesic pathways through the potential energy landscape of a liquid of linear molecules” [J. Chem. Phys. 140, 174503 (2014)]

Cited by 2 publications

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The inherent dynamics of isotropic- and nematic-phase liquid crystals

The inherent dynamics of isotropic- and nematic-phase liquid crystals

What is special about how roaming chemical reactions traverse their potential surfaces? Differences in geodesic paths between roaming and non-roaming events

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