PNNL

Abstract

This paper is a continuation of earlier work for which the high resolution infrared spectrum of [1.1.1]propellane was measured and its k and l structure resolved for the first time. Here we present results from an analysis of more than 16,000 transitions involving three fundamental bands ?10 (E'-A1'), ?11 (E'-A1'), ?14 (A2?-A1') and two difference bands (?10- ?18) (E'-E?) and (?11-?18) (E'-E"). Additional information about ?18 was also obtained from the difference band (?15+?18)-?18 (E'-E") and the binary combination band (?15+?18) (E'-A1'). Through the use of the ground state constants reported in an earlier paper [1], rovibrational constants have been determined for all the vibrational states involved in these bands. The rovibrational parameters for the ?18(E?) state were obtained from combination-differences and showed no need to include interactions with other states. The ?10(E') state analysis was also straight-forward, with only a weak Coriolis interaction with the levels of the ?14(A2?) state. The latter levels are much more affected by a strong Coriolis interaction with the levels of the nearby ?11(E') state and also by a small but significant interaction with another state, presumably the ?16(E?) state, that is not directly observed. Gaussian calculations (B3LYP/cc-pVTZ) computed at the anharmonic level aided the analyses by providing initial values for many of the parameters. These theoretical results generally compare favorably with the final parameter values deduced from the spectral analyses. Finally, evidence was obtained for several level crossings between the rotational levels of the ?11 and ?14 states and, using a weak coupling term corresponding to a ?k = ±5, ?l = ±1 matrix element, it was possible to find transitions from the ground state that, combined with transitions to the same upper state, give a value of C0 = 0.1936519(4) cm-1. This result, combined with the value of B0 = 0.28755833(14) cm-1 reported earlier [1], yields a value of 1.586282(3) ? for the length of the novel axial CC bond in propellane.