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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2 Citations (Scopus)

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

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Electronic states
Photoelectrons
negative ions
Anions
photoelectrons
Negative ions
anions
Derivatives
predictions
electronics
ground state
Ground state
methylene
energy
fragmentation
vapor phases
Lactones
orbitals
Gases
trimethylenemethane

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

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title = "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",
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.",
author = "Bo Chen and Hrovat, {David A.} and Borden, {Weston Thatcher}",
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TY - JOUR

T1 - 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

AU - Chen, Bo

AU - Hrovat, David A.

AU - Borden, Weston Thatcher

PY - 2017/4/1

Y1 - 2017/4/1

N2 - 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.

AB - 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.

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