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Quantum Nuclear Delocalization and its Rovibrational Fingerprints |
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| Authors: | Irén Simkó Christoph Schran Fabien Brieuc Csaba Fábri Oskar Asvany Stephan Schlemmer Dominik Marx Attila G Császár |
| Institution: | 1. Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, ELTE Eötvös Loránd University, H-1117 Budapest, Pázmány Péter sétány 1/A, Hungary;2. Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany
Present address: Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK;3. Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany Present address: Laboratoire Matière en Conditions Extrêmes, Université Paris-Saclay, CEA, DAM, DIF, 91297 Arpajon, France;4. MTA-ELTE Complex Chemical Systems Research Group, H-1117 Budapest, Pázmány Péter sétány 1/A, Hungary;5. I. Physikalisches Institut, Universität zu Köln, Zülpicher Str. 77, 50937 Köln, Germany;6. Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany |
| Abstract: | Quantum mechanics dictates that nuclei must undergo some delocalization. In this work, emergence of quantum nuclear delocalization and its rovibrational fingerprints are discussed for the case of the van der Waals complex  . The equilibrium structure of  is planar and T-shaped, one He atom solvating the quasi-linear He?H+?He core. The dynamical structure of  , in all of its bound states, is fundamentally different. As revealed by spatial distribution functions and nuclear densities, during the vibrations of the molecule the solvating He is not restricted to be in the plane defined by the instantaneously bent  chomophore, but freely orbits the central proton, forming a three-dimensional torus around the  chromophore. This quantum delocalization is observed for all vibrational states, the type of vibrational excitation being reflected in the topology of the nodal surfaces in the nuclear densities, showing, for example, that intramolecular bending involves excitation along the circumference of the torus. |
| Keywords: | nuclear delocalization variational nuclear-motion computations path integral molecular dynamics (PIMD) spatial distribution functions (SDF) nuclear density (ND) |