ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Equation of motion coupled-cluster (EOM-CCSD) predictions of structures and electronic excitation energies for the recently detected Ca+–acetylene π-complex confirm three experimental state assignments, but suggest reinterpretation of the signals associated with the (2) 2B1 and (2) 2B2 states that correlate to the 2P←2S Ca+ atomic transition. The originally assigned 000 band for the (2) 2B1 state corresponds to the computed excitation energy to the (2) 2B2 state and simple reassignment is proposed. The true (2) 2B1 state was not assigned in the original spectrum. However, the computed oscillator strength is large and its optimized geometry is similar to that of the ground state. Furthermore, the experimental band tentatively attributed to the onset of the symmetric C–H stretching progression of the assigned state has a relative energy conspicuously close to the computed electronic energy for the unassigned (2) 2B1 state. Based on the computed energy separations of the optimized EOM-CCSD structures, reassignment of this vibronic band to the 000 line of the (2) 2B1 state is proposed. The newly assigned bands are also compared to the analogous transitions in the beryllium–and magnesium–acetylene π complexes. © 2000 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.481845
