화학공학소재연구정보센터
Journal of Chemical Physics, Vol.103, No.11, 4447-4454, 1995
Vibronic Structure of the Cyclopentadienyl Radical and Its Nonrigid Van-der-Waals Cluster with Nitrogen
Fluorescence excitation and two color mass resolved excitation spectroscopy are employed to study the D-1((2)A"(2))<--D-0((2)E"(1)) vibronic transitions of the cyclopentadienyl radical (cpd) and its van der Waals cluster with nitrogen. The radical is created by photolysis of the cyclopentadiene dimer and cooled by expansion from a supersonic nozzle. The cpd(N-2)(1) cluster is generated in this cooling process. Mass resolved excitation spectra of cpd are obtained for the first 1200 cm(-1) of the D-1<--D-0 transition. The excitation spectrum of cpd(N-2)(1) shows a complicated structure far the origin transition. With the application of hole burning spectroscopy, we are able to assign all the cluster transitions to a single isomer. The features are assigned to a 55 cm(-1) out-of-plane van der Waals mode stretch and contortional (rotational) motions of the N-2 molecule with respect to the cpd radical. Empirical potential energy calculations are used to predict the properties of this cluster and yield the following results : (1) the N-2 molecular axis is perpendicular to the cpd fivefold axis and parallel to the plane of the cpd ring with the two molecular centers of mass lying on the fivefold ring axis; (2) the binding energy of cpd(N-2)(1) is 434 cm(-1); and (3) the rotational motion of the N-2 molecule is essentially unhindered about the cpd fivefold axis. The molecular symmetry group D-5h(MS) is applied to the nonrigid cluster and optical selection rules exclude even<->odd transitions (Delta n=0, +/-2, +/-4,... allowed) between the different contortional levels. Tentative assignments are given to the observed contortional features based on these considerations. The barrier to internal rotation is also small in the excited state. The results for the cpd(N-2)(1) van der Waals cluster are compared to those for the benzene (N-2)(1) and benzyl radical (N-2)(1) clusters.