Rovibronic structure in slow photoelectron velocity-map imaging spectroscopy of CH2CN- and CD2CN-

Marissa L. Weichman, Jongjin B. Kim, Daniel M. Neumark

Research output: Contribution to journalArticle

14 Scopus citations

Abstract

We report high-resolution anion photoelectron spectra of the cryogenically cooled cyanomethide anion, CH2CN-, and its isotopologue, CD2CN-, using slow photoelectron velocity-map imaging (SEVI) spectroscopy. Electron affinities of 12 468(2) cm-1 for CH2CN and 12 402(2) cm-1 for CD2CN are obtained, demonstrating greater precision than previous experiments. New vibrational structure is resolved for both neutral species, especially activity of the ν5 hydrogen umbrella modes. The ν6 out-of-plane bending mode fundamental frequency is measured for the first time in both systems and found to be 420(10) cm-1 for CH2CN and 389(8) cm-1 for CD2CN. Some rotational structure is resolved, allowing for accurate extraction of vibrational frequencies. Temperature-dependent SEVI spectra show marked effects ascribed to controlled population of low-lying anion vibrational levels. We directly measure the inversion splitting between the first two vibrational levels of the anion ν5 umbrella mode in both species, finding a splitting of 130(20) cm-1 for CH2CN- and 81(20) cm-1 for CD2CN-. Franck-Condon forbidden activity is observed and attributed to mode-specific vibrational autodetachment from the CH 2CN- and CD2CN- dipole bound excited states. We also refine the binding energy of the anion dipole bound states to 39 and 42 cm-1, respectively, for CH2CN- and CD2CN-.

Original languageEnglish (US)
Article number104305
JournalJournal of Chemical Physics
Volume140
Issue number10
DOIs
StatePublished - Mar 14 2014
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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