The van der Waals (vdW) complexes consisting of benzonitrile and various partner species were formed in a free jet and their laserhyphen;induced fluorescence (LIF) spectra were recorded. For all the species chosen as partners (Ar, Kr, N2O, CF3H, and H2O), the LIF spectra showed a red shift relative to that of benzonitrile monomer. The spectral shift increased with increasing dipole moment of the partner species owing to the large dipolendash;dipole interaction between the partner species and benzonitrile whose dipole moment amounts to 4.14 D. With the aid of computer simulation, the rotational contours of the LIF spectra of the benzonitrile dimer and benzonitrilendash;Ar complex were analyzed. The dimer was found to be in planar form with the two CN groups facing each other in an antiparallel geometry, whereas in the Ar complex the Ar atom lies over the benzene ring slightly leaning toward the CN group.
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