TY - JOUR
T1 - Electronic structures of aziridenium and cyclopropylidene. Hypovalent atoms in three-membered rings
AU - Cramer, Chris
AU - Worthington, Sharon E.
PY - 1995/1/1
Y1 - 1995/1/1
N2 - Hartree - Fock, second-order perturbation theory, configuration interaction including single and double excitations, coupled cluster theory including singles, doubles, and perturbative triples, multiconfiguration self-consistent-field, and density functional calculations have been carried out using large basis sets for the 1A1 and 3B1 electronic states of aziridenium and cyclopropylidene. The aziridenium ion is predicted to be a ground state triplet with a singlet-triplet gap of 10.7 ± 0.4 kcal/mol; the singlet is a transition state subject to ring opening. Isoelectronic cyclopropylidene is predicted to be a ground state singlet with a singlet-triplet gap of -13.8 ± 0.3 kcal/mol. The optimized aziridenium triplet geometry manifests a remarkably long carbon-carbon bond (1.745 Å at the MCSCF level); the corresponding bond distance in cyclopropylidene is also long (1.618 Å).
AB - Hartree - Fock, second-order perturbation theory, configuration interaction including single and double excitations, coupled cluster theory including singles, doubles, and perturbative triples, multiconfiguration self-consistent-field, and density functional calculations have been carried out using large basis sets for the 1A1 and 3B1 electronic states of aziridenium and cyclopropylidene. The aziridenium ion is predicted to be a ground state triplet with a singlet-triplet gap of 10.7 ± 0.4 kcal/mol; the singlet is a transition state subject to ring opening. Isoelectronic cyclopropylidene is predicted to be a ground state singlet with a singlet-triplet gap of -13.8 ± 0.3 kcal/mol. The optimized aziridenium triplet geometry manifests a remarkably long carbon-carbon bond (1.745 Å at the MCSCF level); the corresponding bond distance in cyclopropylidene is also long (1.618 Å).
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U2 - 10.1021/j100005a015
DO - 10.1021/j100005a015
M3 - Article
AN - SCOPUS:0001160501
VL - 99
SP - 1462
EP - 1465
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 5
ER -