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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U2 - 10.1002/poc.3594

DO - 10.1002/poc.3594

M3 - Article

AN - SCOPUS:85028283110

VL - 30

JO - Journal of Physical Organic Chemistry

JF - Journal of Physical Organic Chemistry

SN - 0894-3230

IS - 4

M1 - e3594

ER -