Vibrational relaxation in jet-cooled alkyl benzenes. I.Absorption spectra

Abstract

Fluorescence excitation spectra of a series of alkylbenzenes cooled in a supersonic free jet have been obtained for the first 1000 cm⁻¹ region of the ¹B₂(ππ*)←¹A₁ ultraviolet absorption spectrum. The series includes all n‐alkylbenzenes up to n‐hexyl together with isopropyl‐ and tert‐butylbenzene. As with toluene, the spectra in this region for all alkylbenzenes is found to be dominated by vibrations of five ring modes: 6a, 6b, 1, 12, and 18a. Three of these—the ’’system modes’’ (6b, 12, 18a)—are found to be largely invariant to changes in the alkyl chain length and type— the ’’bath.’’ For n‐alkylbenzenes with chain length of three or higher, spectra of two distinct conformations are observed with roughly equal intensity. These conformations are distinguished by configuration about the 1–2 carbon–carbon bond of the alkyl chain. When this configuration is trans [n‐(t)‐alkylbenzene], the alkyl chain extends away from the phenyl ring leaving the ring free to van der Waals complex binding on both sides of the ring. The He₂–n‐(t)‐alkylbenzene van der Waals complex is thus observed. When the conformation about the 1–2 bond is gauche [n‐(g)‐alkylbenzene] the alkyl chain partially covers one side of the phenyl ring. This produces a small red‐shift of the spectrum (a self‐induced solvent shift) and prohibits the formation of the ring‐centered dihelium van der Waals complex.