Rotational spectra of four of the five conformers of 1-pentene

The rotational spectra of four of the five expected conformers of 1-pentene, together with their monosubstituted C-13 isotopic forms, have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. One of the conformers has C-s point-group symmetry while the other three conformers have C-1 point-group symmetry. The measurements are compared to results from molecular modeling calculations using the MM3 molecular-mechanics force field of Allinger and to ab initio electronic structure calculations (MP2/6-31G*, MP2/6-311G*, MP4/6-31G*, MP4/6-311G*). Both types of calculations suggest the existence of five distinct conformers of 1-pentene, four of C-1 symmetry and one of C-s symmetry. Both the MM3 and ab initio rotational constants deviate from the measured values by less than or equal to 5%. The relatively high barriers between the four conformers limit the conformational cooling in the expansion, allowing all four conformers to be observed at the < 2 K rotational temperature of the molecular beam. Efforts to identify the fifth conformer were unsuccessful, presumably due to its reduced intensity, which makes it difficult to identify its spectral pattern from among the plethora of weak unassigned lines due to impurities, complexes, and possible vibrationally excited conformers. The fifth conformer is predicted to have the highest energy of the five conformers of 1-pentene, as well as a low-energy barrier (109 cm(-1) at MP2/6-311G* level) for conformational isomerization. (C) 2000 American Institute of Physics. [S0021-9606(00)00514-6].