A global potential energy surface for H3+
| Autor: | Irina I. Mizus, Jonathan Tennyson, Laura K. McKemmish, Oleg L. Polyansky, Alexander Alijah, Nikolai F. Zobov |
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| Přispěvatelé: | Department of Physics and Astronomy [UCL London], University College of London [London] (UCL), Groupe de spectrométrie moléculaire et atmosphérique (GSMA), Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS), Institute of Applied Physics, Russian Academy of Sciences |
| Rok vydání: | 2018 |
| Předmět: |
[PHYS.MPHY]Physics [physics]/Mathematical Physics [math-ph]
Biophysics FOS: Physical sciences 010402 general chemistry 01 natural sciences Dissociation (chemistry) Physics - Chemical Physics 0103 physical sciences Physics::Atomic and Molecular Clusters [CHIM]Chemical Sciences Wavenumber Physics::Chemical Physics Physical and Theoretical Chemistry Adiabatic process Molecular Biology Root-mean-square deviation ComputingMilieux_MISCELLANEOUS Chemical Physics (physics.chem-ph) Physics 010304 chemical physics Polyatomic ion Rotational–vibrational spectroscopy Condensed Matter Physics Bond-dissociation energy 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Potential energy surface Atomic physics |
| Zdroj: | Molecular Physics Molecular Physics, Taylor & Francis, 2018, 117 (13), pp.1663-1672. ⟨10.1080/00268976.2018.1554195⟩ |
| ISSN: | 1362-3028 0026-8976 |
| DOI: | 10.1080/00268976.2018.1554195 |
| Popis: | A globally correct potential energy surface (PES) for the \hp\ molecular ion is presented. The Born-Oppenheimer (BO) \ai\ grid points of Pavanello et. al. [\textit{J. Chem. Phys.} {\bf 136}, 184303 (2012)] are refitted as BOPES75K, which reproduces the energies below dissociation with a root mean square deviation of 0.05~\cm; points between dissociation and 75\,000 \cm\ are reproduced with the average accuracy of a few wavenumbers. The new PES75K+ potential combines BOPES75K with adiabatic, relativistic and quantum electrodynamics (QED) surfaces to provide the most accurate representation of the \hp\ global potential to date, overcoming the limitations on previous high accuracy H$_3^+$ PESs near and above dissociation. PES75K+ can be used to provide predictions of bound rovibrational energy levels with an accuracy of approaching 0.1~\cm. Calculation of rovibrational energy levels within PES75K+ suggests that the non-adiabatic correction remains a limiting factor. The PES is also constructed to give the correct asymptotic limit making it suitable for use in studies of the H$^+$\,+\,H$_2$ prototypical chemical reaction. An improved dissociation energy for H$_3^+$ is derived as $D_0\,=\,$35\,076\,$\pm\,2\,$cm$^{-1}$. Comment: 20 pages, 4 figures, 6 tables |
| Databáze: | OpenAIRE |
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