Adiabatic interaction leading to the avoided crossing between the twin 31δg and 41δg rydberg states in na2

Thou Jen Whang, Chanchal Chaudhuri, Ray Yuan Chang, Wei Xiang Chen, Chin Chun Tsai

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We present detailed investigations of our previously reported observations of the 31δg and 41δg Rydberg states having separated-atom limits of Na(3s) + Na(4d) and Na(3s) + Na(4f), respectively, of Na2 using high-resolution cw optical-optical double resonance spectroscopic measurements and analyzing the assigned rovibrational energy levels both by the individual linear fit method and the Dunham polynomial fit method. We have sorted out e/f-parity observed energy levels, and then from the Dunham polynomial fits of the e-parity levels, we have derived molecular constants and constructed Rydberg-Klein-Rees potentials of the 31Ag and 41Ag states, which appear to be twin states with an avoided crossing at Rc = 4.10 A and a splitting of Ac = 94 cm-1. The potentials are in good agreement with the ab initio calculations and linear fit results. The A-doubling splittings and the (f-d) l-mixing are investigated. A detailed discussion is focused on the adiabatic interaction of the perturbed molecular wave functions/states causing mutual amplitude/intensity sharing giving rise to avoided crossing between the 31Ag and 41Ag states.

Original languageEnglish
Pages (from-to)4954-4962
Number of pages9
JournalJournal of Physical Chemistry A
Issue number17
Publication statusPublished - 2009 Apr 30

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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