Symmetry breaking in the cyclic C(3)C(2)H radical.
We have employed high-level coupled cluster methods including connected triple excitations to study the possibility of symmetry-breaking in the (2)B(2) ground state of the c-C(3)C(2)H radical. Specifically, we find that spin-restricted open-shell Hartree-Fock (ROHF) reference orbitals yield a C(2v) structure, whereas spin-unrestricted Hartree-Fock (UHF) and Brueckner orbitals lead to a symmetry-broken C(s) minimum-energy geometry. Equation-of-motion coupled cluster singles and doubles method for ionized states yields a C(s) structure with a double-zeta basis set, but not with a triple-zeta basis set. Through a detailed analysis of the orbital instability/near-instability behavior of each type of Hartree-Fock reference, we have determined that the UHF reference wave function is more reliable than the ROHF reference in this case and that the Born-Oppenheimer potential surface for c-C(3)C(2)H exhibits a symmetry broken C(s) global minimum. This result is supported by excited-state computations, which indicate that a second-order (pseudo) Jahn-Teller interaction is responsible for the symmetry-breaking.
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, USA.
Benjamin
B
Mintz
T Daniel
TD
Crawford