CEQUINOR   05415
CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Unidad Ejecutora - UE
artículos
Título:
Spectroscopic, Structural and Theoretical Studies on Matrix Photochemistry at Low Temperatures and Spectroscopic Properties of ã-Butyrothiolactone
Autor/es:
NAHIR DUGARTE; MAURICIO F. ERBEN; ROSANA M. ROMANO; MAOFA GE; LI YAO; CARLOS O. DELLA VéDOVA
Revista:
JOURNAL OF PHYSICAL CHEMISTRY A
Editorial:
AMER CHEMICAL SOC
Referencias:
Año: 2010 vol. 114 p. 9462 - 9462
ISSN:
1089-5639
Resumen:
The five-membered heterocyclic ã-butyrothiolactone was isolated in a low-temperature, inert Ar matrix, and the UV-visible (200 e ë e 800 nm)-induced photochemistry was studied. On the basis of the IR spectra, the formation of ethylketene (CH3CH2CHdCdO) was identified as the main channel of photodecomposition. The valence electronic structure was investigated by He(I) photoelectron spectroscopy assisted by quantum chemical calculations at the outer valence Green’s function/6-311++G(d,p) level of theory. The first three bands at 9.54, 9.69, and 11.89 eV are assigned to the nS, nO, and ðCdO orbitals, respectively, denoting the importance of the -SC(O)- group in the outermost electronic properties. The conventional ring strain energy was determined to be 3.8 kcal mol-1 at the G2MP2 level of calculation within the hyperhomodesmotic model.ã-butyrothiolactone was isolated in a low-temperature, inert Ar matrix, and the UV-visible (200 e ë e 800 nm)-induced photochemistry was studied. On the basis of the IR spectra, the formation of ethylketene (CH3CH2CHdCdO) was identified as the main channel of photodecomposition. The valence electronic structure was investigated by He(I) photoelectron spectroscopy assisted by quantum chemical calculations at the outer valence Green’s function/6-311++G(d,p) level of theory. The first three bands at 9.54, 9.69, and 11.89 eV are assigned to the nS, nO, and ðCdO orbitals, respectively, denoting the importance of the -SC(O)- group in the outermost electronic properties. The conventional ring strain energy was determined to be 3.8 kcal mol-1 at the G2MP2 level of calculation within the hyperhomodesmotic model.-visible (200 e ë e 800 nm)-induced photochemistry was studied. On the basis of the IR spectra, the formation of ethylketene (CH3CH2CHdCdO) was identified as the main channel of photodecomposition. The valence electronic structure was investigated by He(I) photoelectron spectroscopy assisted by quantum chemical calculations at the outer valence Green’s function/6-311++G(d,p) level of theory. The first three bands at 9.54, 9.69, and 11.89 eV are assigned to the nS, nO, and ðCdO orbitals, respectively, denoting the importance of the -SC(O)- group in the outermost electronic properties. The conventional ring strain energy was determined to be 3.8 kcal mol-1 at the G2MP2 level of calculation within the hyperhomodesmotic model.3CH2CHdCdO) was identified as the main channel of photodecomposition. The valence electronic structure was investigated by He(I) photoelectron spectroscopy assisted by quantum chemical calculations at the outer valence Green’s function/6-311++G(d,p) level of theory. The first three bands at 9.54, 9.69, and 11.89 eV are assigned to the nS, nO, and ðCdO orbitals, respectively, denoting the importance of the -SC(O)- group in the outermost electronic properties. The conventional ring strain energy was determined to be 3.8 kcal mol-1 at the G2MP2 level of calculation within the hyperhomodesmotic model.++G(d,p) level of theory. The first three bands at 9.54, 9.69, and 11.89 eV are assigned to the nS, nO, and ðCdO orbitals, respectively, denoting the importance of the -SC(O)- group in the outermost electronic properties. The conventional ring strain energy was determined to be 3.8 kcal mol-1 at the G2MP2 level of calculation within the hyperhomodesmotic model.S, nO, and ðCdO orbitals, respectively, denoting the importance of the -SC(O)- group in the outermost electronic properties. The conventional ring strain energy was determined to be 3.8 kcal mol-1 at the G2MP2 level of calculation within the hyperhomodesmotic model.-SC(O)- group in the outermost electronic properties. The conventional ring strain energy was determined to be 3.8 kcal mol-1 at the G2MP2 level of calculation within the hyperhomodesmotic model.-1 at the G2MP2 level of calculation within the hyperhomodesmotic model.