The rotational structure of the vibrationless S1←S0 transition of pentacene has been investigated using a strongly collimated seeded supersonic argon beam. Because single rotational lines could not be completely resolved, a band contour analysis was performed. The rotational constants of the electronic ground state X 1A1g were found to be under the asymmetric rotor approximation A″=1320.6(9), B″=117.97(9), C″=108.28(15) MHz, whereas the differences to the first electronic excited state A 1B2u are ΔA=A′−A″=13.2(3), ΔB=−0.764(45), ΔC=−0.54(6) MHz. A new value of the band origin was determined to be ν00=18 648.996(4) cm−1 and the band type was confirmed to be of type b as proposed by symmetry arguments. Good agreement between observed and calculated spectra was obtained assuming planarity in both ground and excited state. From the fit procedure a rotational temperature of about 7 K was deduced. The nuclear statistical weights of the electronic ground state are reported.

The 1s photoionization of atomic Li was studied by photoelectron spectroscopy in the photon energy region between 85 and 140 eV for the ground state and the three lowest excited configurations Li(*) 1s(2)nl, nl=2p, 3s, 3p. The importance of electron correlations was investigated by comparing the multielectron transitions, so-called shake-up and conjugate shake-up satellites, and the direct process, so-called main lines. The relative intensity of the satellites increases with the level of initial excitation of the Li atom. The shake-up process dominates for states with an n=3 valence electron and the satellites become stronger than the main lines. This spectacular effect can be explained by the spatial overlap of the initial and final state wave functions. Surprisingly, the spatial overlap affects shake-up and conjugate shake-up lines in the same way.

Partial 3d5/2 photoionization cross sections of atomic Cs and Ba as well as the asymmetry parameter beta of the angular distribution of the Cs 3d5/2 photoelectrons were investigated near the threshold of the 3d3/2 channel at about 750 eV and 800 eV, respectively. Strong electron correlations, in particular, the spin-orbit activated interchannel coupling between the 3d5/2 and 3d3/2 channels, govern the observed spectra. The most striking effect was found for beta5/2 of Cs with a dramatic increase from beta=1.0 to beta=1.5 in the energy region where the mixing between both channels causes a pronounced minimum in the partial 3d5/2 cross section. This result indicates the decisive influence of the interference term on the asymmetry parameter beta with its dependence on the phase difference between the outgoing p and f waves.

Photoelectron spectra of atomic potassium excited by laser optical pumping into the 3p64p2P1/2 and 2P3/2 states are measured with high-energy resolution. The relative intensities of the 3p54p fine-structure lines depend strongly on the initial excitation to one of the 4p spin–orbit components. Similar to the case of sodium, dynamically and quasiforbidden transitions are observed in the photoelectron spectra of potassium. The theoretical predictions of the generalized geometrical model are in excellent agreement with the experimental data.

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