Ultrahigh-resolution laser spectroscopy of the S1B2u ← S0Ag transition of perylene

A rotationally resolved ultrahigh-resolution fluorescence excitation spectrum of the S₁ ← S₀ transition of perylene has been observed using a collimated supersonic jet technique in conjunction with a single-mode UV laser. We assigned 1568 rotational lines of the band, and accurately determined the rotational constants. The obtained value of inertial defect was positive, accordingly, the perylene molecule is considered to be planar with D_2h symmetry. We determined the geometrical structure in the S₀ state by ab initio theoretical calculation at the RHF/6-311+G(d,p) level, which yielded rotational constant values approximately identical to those obtained experimentally. Zeeman broadening of each rotational line with the external magnetic field was negligibly small, and the mixing with the triplet state was shown to be very small. This evidence indicates that intersystem crossing (ISC) in the S₁¹B_2u state is very slow. The rate of internal conversion (IC) is also inferred to be small because the fluorescence quantum yield is high. The rotational constants of the S₁¹B_2u state were very similar to those of the S₀¹A_g state. The slow internal conversion (IC) at the S₁ zero-vibrational level is attributed to a small structural change upon electronic transition.