Premium
Calculations of the energies of the low‐lying electronic states of dioxatrimethylenemethane (H 2 CCO 2 ) and prediction of the negative ion photoelectron (NIPE) spectrum of its radical anion
Author(s) -
Chen Bo,
Hrovat David A.,
Borden Weston Thatcher
Publication year - 2017
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3594
Subject(s) - chemistry , singlet state , ion , open shell , ground state , atomic physics , triplet state , basis set , unpaired electron , atom (system on chip) , methylene , computational chemistry , density functional theory , molecule , excited state , physics , organic chemistry , computer science , embedded system
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 b 2 σ MO and the other a b 1 π MO. An open‐shell singlet state, with the same orbital occupancy as the triplet, is calculated to lie very close to the 3 A 2 ground state. However, this open‐shell singlet ( 1 A 2 ) 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 CH 2 + CO 2 . 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. Copyright © 2016 John Wiley & Sons, Ltd.