Photolysis production and spectroscopic investigation of the highest vibrational states in H2 (x1σg+ v = 13, 14)

W. Ubachs*, K. F. Lai, M. Beyer, E. J. Salumbides

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


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 languageEnglish
Pages (from-to)1221-1228
Number of pages8
JournalJournal of Physical Chemistry A
Issue number5
Early online date27 Jan 2021
Publication statusPublished - 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 2021 Elsevier B.V., All rights reserved.


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