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Title:Observing quantum monodromy: an energy-momentum map built from experimentally-determined level energies obtained from the ⱱ7 far-infrared band system of ncncs
Author(s):Tokaryk, Dennis W.
Contributor(s):Billinghurst, Brant E.; De Lucia, Frank C.; Winnewisser, Manfred; Winnewisser, Brenda P.; Ross, Stephen Cary
Subject(s):Spectroscopy of Large Amplitude Motions
Abstract:The concept of Quantum Monodromy (QM) provides a fresh insight into the structure of rovibrational levels in those flexible molecules for which a bending mode can carry the molecule through the linear configuration. To confirm the existence of QM in a molecule required the fruits of several strands of development: the formulation of the abstract mathematical concept of monodromy, including the exploration of its relevance to systems described by classical mechanics and its manifestation in quantum molecular applications
the development of the required spectroscopic technology and computer-aided assignment
and the development of a theoretical model to apply in fitting to the observed data. We present a timeline for each of these strands, converging in our initial confirmation of QM in NCNCS from pure rotational data alone.\footnote{B. P. Winnewisser \emph{et al.}, Phys. Rev. Lett. \textbf{95}, 243002 (2005).} In that work a Generalised SemiRigid Bender (GSRB) Hamiltonian was fitted to the experimental rotational structure. Rovibrational energies calculated from the fitted GSRB parameters allowed us to construct an ``Energy-Momentum" map and confirm the presence of QM in NCNCS. In further experimental work at the Canadian Light Source Synchrotron we have identified a network of transitions directly connecting the relevant energy levels and thereby have produced a refined Energy Momentum map for NCNCS from experimental measurements alone. This map extends from the ground vibrational level to well above the potential energy barrier, beautifully illustrating the characteristic signature of QM in a system uncomplicated by interaction with other vibrational modes.
Issue Date:2016-06-20
Publisher:International Symposium on Molecular Spectroscopy
Genre:Conference Paper/Presentation
Rights Information:Copyright 2016 by the authors
Date Available in IDEALS:2017-01-26

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