Non-Adiabatic Effects on Excited States of Vinylidene Observed with Slow Photoelectron Velocity-Map Imaging

Jessalyn A. Devine, Marissa L. Weichman, Xueyao Zhou, Jianyi Ma, Bin Jiang, Hua Guo, Daniel M. Neumark

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High-resolution slow photoelectron velocity-map imaging spectra of cryogenically cooled X2B2 H2CC- and D2CC- in the region of the vinylidene triplet excited states are reported. Three electronic bands are observed and, with the assistance of electronic structure calculations and quantum dynamics on ab initio-based near-equilibrium potential energy surfaces, are assigned as detachment to the ã 3B2 (T1), b 3A2 (T2), and à 1A2 (S1) excited states of neutral vinylidene. This work provides the first experimental observation of the à singlet excited state of H2CC. While regular vibrational structure is observed for the ã and à electronic bands, a number of irregular features are resolved in the vicinity of the b band vibrational origin. High-level ab initio calculations suggest that this anomalous structure arises from a conical intersection between the ã and b triplet states near the b state minimum, which strongly perturbs the vibrational levels in the two electronic states through nonadiabatic coupling. Using the adiabatic electron affinity of H2CC previously measured to be 0.490(6) eV by Ervin and co-workers [J. Chem. Phys. 1989, 91, 5974], term energies for the excited neutral states of H2CC are found to be T03B2) = 2.064(6), T0(b 3A2) = 2.738(6), and T01A2) = 2.991(6) eV.

Original languageEnglish (US)
Pages (from-to)16417-16425
Number of pages9
JournalJournal of the American Chemical Society
Issue number50
StatePublished - Dec 21 2016
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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