Giessener Elektronische Bibliothek

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Saddle point localization of molecular wavefunctions

Mellau, Georg Ch ; Kyuberis, Alexandra A. ; Polyansky, Oleg L. ; Zobov, Nikolai ; Field, Robert W.


Originalveröffentlichung: (2016) Scientific Reports 6:33068 doi: 10.1038/srep33068
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URN: urn:nbn:de:hebis:26-opus-137705
URL: http://geb.uni-giessen.de/geb/volltexte/2018/13770/

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Sammlung: Open Access - Publikationsfonds
Universität Justus-Liebig-Universität Gießen
Institut: Physikalisch-Chemisches Institut
Fachgebiet: Physik
DDC-Sachgruppe: Physik
Dokumentart: Aufsatz
Sprache: Deutsch
Erstellungsjahr: 2016
Publikationsdatum: 11.10.2018
Kurzfassung auf Deutsch: The quantum mechanical description of isomerization is based on bound eigenstates of the molecular potential energy surface. For the near-minimum regions there is a textbook-based relationship between the potential and eigenenergies. Here we show how the saddle point region that connects the two minima is encoded in the eigenstates of the model quartic potential and in the energy levels of the [H, C, N] potential energy surface. We model the spacing of the eigenenergies with the energy dependent classical oscillation frequency decreasing to zero at the saddle point. The eigenstates with the smallest spacing are localized at the saddle point. The analysis of the HCN???HNC isomerization states shows that the eigenstates with small energy spacing relative to the effective (v1, v3, l) bending potentials are highly localized in the bending coordinate at the transition state. These spectroscopically detectable states represent a chemical marker of the transition state in the eigenenergy spectrum. The method developed here provides a basis for modeling characteristic patterns in the eigenenergy spectrum of bound states.
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