Abstract
Rovibrational quantum states in the X1Σg+ electronic ground state of H2 are prepared in the v = 13 vibrational level up to its highest bound rotational level J = 7, and in the highest bound vibrational level v = 14 (for J = 1) by two-photon photolysis of H2S. These states are laser-excited in a subsequent two-photon scheme into F1Σg+ outer well states, where the assignment of the highest (v,J) states is derived from a comparison of experimentally known levels in F1Σg+, combined with ab initio calculations of X1Σg+ levels. The assignments are further verified by excitation of F1Σg+ population into autoionizing continuum resonances, which are compared with multichannel quantum defect calculations. Precision spectroscopic measurements of the F-X intervals form a test for the ab initio calculations of ground state levels at high vibrational quantum numbers and large internuclear separations, for which agreement is found.
Original language | English |
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Pages (from-to) | 1221-1228 |
Number of pages | 8 |
Journal | Journal of Physical Chemistry A |
Volume | 125 |
Issue number | 5 |
Early online date | 27 Jan 2021 |
DOIs | |
Publication status | Published - 11 Feb 2021 |
Bibliographical note
Funding Information:The authors thank Dr. Christian Jungen for fruitful discussions and for making available his MQDT-codes for calculating and assigning the autoionization resonances. W.U. acknowledges the European Research Council for an ERC Advanced Grant (No. 670168).
Publisher Copyright:
© 2021 The Authors. Published by American Chemical Society
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
Funding
The authors thank Dr. Christian Jungen for fruitful discussions and for making available his MQDT-codes for calculating and assigning the autoionization resonances. W.U. acknowledges the European Research Council for an ERC Advanced Grant (No. 670168).
Funders | Funder number |
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Horizon 2020 Framework Programme | 670168 |