TY - JOUR
T1 - Theory and experiment in accord
T2 - the vinylidene radical cation
AU - Frenking, Gernot
PY - 1989/12/1
Y1 - 1989/12/1
N2 - Using ab initio calculations based on electronic structure theory, the activation barrier of the 2B1 ground state of the vinylidene cation radical 3 for rearrangement to the 2Πu acetylene ground state ion 2 is predicted to be 9.4 kcal mol-1 [MP4/6-311G(d,p)//HF/6-31G(d)]. At the same level of theory, the 2A1 excited state of H2CC+{radical dot} 4 is calculated to rearrange without a barrier to 2. In contrast to the doublet states, the activation barrier for hydrogen migration of the lowest-lying 4A2 quartet state of H2CC+{radical dot} 5 is predicted to be very high (57.2 kcal mol-1). It is concluded that the experimentally observed long-living vinylidene cation radical is probably 5.
AB - Using ab initio calculations based on electronic structure theory, the activation barrier of the 2B1 ground state of the vinylidene cation radical 3 for rearrangement to the 2Πu acetylene ground state ion 2 is predicted to be 9.4 kcal mol-1 [MP4/6-311G(d,p)//HF/6-31G(d)]. At the same level of theory, the 2A1 excited state of H2CC+{radical dot} 4 is calculated to rearrange without a barrier to 2. In contrast to the doublet states, the activation barrier for hydrogen migration of the lowest-lying 4A2 quartet state of H2CC+{radical dot} 5 is predicted to be very high (57.2 kcal mol-1). It is concluded that the experimentally observed long-living vinylidene cation radical is probably 5.
UR - http://www.scopus.com/inward/record.url?scp=0007657805&partnerID=8YFLogxK
U2 - 10.1016/0168-1176(89)83049-6
DO - 10.1016/0168-1176(89)83049-6
M3 - 文章
AN - SCOPUS:0007657805
SN - 0168-1176
VL - 95
SP - 109
EP - 118
JO - International Journal of Mass Spectrometry and Ion Processes
JF - International Journal of Mass Spectrometry and Ion Processes
IS - 1
ER -