Electronic absorption spectra of ion-radicals of butadiene and methyl substituted butadienes

Radical Cations of Monomethyl-Substituted 1,3-Butadienes: Resonance Raman Spectra and Molecular Orbital Calculations

“…The monomethyl-substituted 1,3-butadiene radical cations have been the subject of various spectroscopic investigations in the past. The electronic absorption spectra of the radiolytically generated cations were measured in glassy matrices − and in solution . The ESR spectra of the radical cations were determined in low-temperature matrices. , The photoelectron spectra of trans - and cis -1,3-pentadiene and isoprene were recorded by various groups, − revealing the electronic states of the radical cations that are accessible by the removal of one electron from the neutral molecule.…”

“…To our best knowledge, the present paper reports the first investigation of the radical cations of cis -1,3-pentadiene and isoprene by vibrational spectroscopy. On the theoretical side, while in some studies the interpretation of the experimental spectra was assisted by semiempirical molecular orbital calculations, ,,,,, detailed molecular orbital calculations of the geometrical, electronic, and vibrational structures of these radical cations have not been reported in the literature. We have performed molecular orbital calculations to help the assignment of the resonance Raman spectra, and in the present article we also report the results of these calculations.…”

“…8 The monomethyl-substituted 1,3-butadiene radical cations have been the subject of various spectroscopic investigations in the past. The electronic absorption spectra of the radiolytically generated cations were measured in glassy matrices [9][10][11][12] and in solution. 13 The ESR spectra of the radical cations were determined in low-temperature matrices.…”

“…, νCdC (32), νCsC(18) 1596 1576 rCH (28), νCdC (28), νCsC (17), dCCC(9) 1513 sCH2 (39), νCdC (19), rCH (16) 1536 sCH2 (34), rCH(27), νCdC (19), νCdC (11) 1447 1472 dCH3 (44), sCH2(27) 1468 dCH3(59), rCH (11), νCsC(10) 1413 rCH (45), dCH3 (20), dCCC (15) 1450 rCH(37), sCH2 (32) (25), νCsC (20) 1564 1551 νCdC (36), sCH2 (29), νCsC (19), rCH (11) 1505 rCH (27), dCH3(18), sCH2 (15), dCCC (14), νCdC (13) 1528 νCdC (25), rCH (24), dCCC (12) 1473 1491 sCH2 (46), rCH (28) 1473 1484 rCH (42), sCH2 (15), νCsC (13), dCH3 (12) 1429 rCH (36) (51), νCsCH3 (21), νCsC (14) 963 952 rCH2 (57), νCsCH3 (20), νCsC (16) 784 νCsCH3 (50), νCsC (26), νCdC (11) 797 νCsCH3 (34), νCsC (25), rCH2 …”

“…Chemistry. This work was partially supported by a grant from (20), νCsC( 16) 784 νCsCH3 (50), νCsC (26), νCdC (11) 797 νCsCH3 (34), νCsC (25)…”