Calculations of the energies of the low-lying electronic states of dioxatrimethylenemethane (H2CCO2) and prediction of the negative ion photoelectron (NIPE) spectrum of its radical anion

Bo Chen, David A. Hrovat, Weston Thatcher Borden

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3 Scopus citations

Abstract

In order to predict the energies of the low-lying electronic states of the dioxa derivative of trimethylenemethane (DOTMM), we have carried out (U)B3LYP, CASPT2, and (U)CCSD(T) calculations, using the aug-cc-pVTZ basis set. Our calculations predict that DOTMM has a triplet ground state, with one unpaired electron occupying a b2 σ MO and the other a b1 π MO. An open-shell singlet state, with the same orbital occupancy as the triplet, is calculated to lie very close to the 3A2 ground state. However, this open-shell singlet (1A2) is predicted to be the transition structure for methylene rotation and to lead to the barrierless formation of an equivalent pair of α-lactones. We also report the results of some calculations on the fragmentation of DOTMM to CH2 + CO2. Our predictions about DOTMM could be tested experimentally by generating the DOTMM•− radical anion in the gas phase and obtaining its negative ion photoelectron spectrum.

Original languageEnglish (US)
Article numbere3594
JournalJournal of Physical Organic Chemistry
Volume30
Issue number4
DOIs
StatePublished - Apr 1 2017

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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