Vibrational wave packets in the B1Πu and D1Σu+ states of Cs2: Determination of improved Cs2+(X) and Cs2(B) spectroscopic constants

A. L. Oldenburg, P. C. John, J. G. Eden

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Abstract

Vibrational wave packets in the B 1Πu and D 1Σu+ excited states of Cs2 have been studied on the ∼100 fs time scale by pump-probe laser spectroscopy. The temporal behavior of the wave packets was monitored by photoionizing the electronically excited molecule with a time-delayed probe pulse and recording the time and energy-integrated photoelectron signal as a function of time delay between the pump and probe pulses. For the B 1Σu+ experiments, wave packets were produced by exciting the B 1Σu+ ← X 1Σg+ transition in the ∼740-790 nm region and subsequently detected by photoionizing the molecule at wavelengths between 565 nm and 600 nm. By simulating the experimentally observed transients with the density matrix formalism (and explicitly accounting for laser chirp and |Δv|>1 coherences), improved values for the equilibrium internuclear separation for the Cs2(B 1Πu) state and Te for the Cs2+(X) state were determined to be Re(B 1Πu) = 4.93 ±0.03 Å and Te[Cs2+(X)] = 29 930± 100 cm-1, respectively. Similar experiments were conducted for the D 1Σu+ state. Wave packets composed of vibrational levels (v′ ≈ 40-50). perturbed by the bound 2 3Πou state were produced on the D 1Σu+ potential surface by driving the D 1Σu+ ←X1Σg+ transition in the 575-610 nm spectral interval.

Original languageEnglish (US)
Pages (from-to)11009-11018
Number of pages10
JournalJournal of Chemical Physics
Volume113
Issue number24
StatePublished - Dec 22 2000

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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