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High-resolution (2+1) resonance-enhanced excited-state photoelectron spectroscopy on supersonic jet expansions of pure C2H4 and C2D4 has been employed to investigate the spectroscopy and dynamics of the lowest excited 11B3u(π,3s) Rydberg state, as well as the 11B1g(π,3py), 11B2g(π,3pz), and 21Ag(π,3px) Rydberg states of ethylene. In combination with ab initio calculations, this approach has for the 11B3u(π,3s) Rydberg state confirmed the majority of previous assignments in the two-photon excitation spectrum but, at the same time, has demonstrated that the hypothesis of a vibronic coupling between this state and the Jahn−Teller distorted 11B2g(π*,3s) state should be discarded. The resonances on which this hypothesis was based are in the present study shown to arise from excitation of the ν3(ag) vibrational mode. For the 3p Rydberg manifold, the present study has for the first time been able to determine unambiguously the 0−0 transitions to all three (π,3p) Rydberg states and to disentangle the vibrational ...

The lowest excited singlet states of 4-(dimethylamino)-4‘-cyanostilbene (DCS), 4-(dimethylamino)-4‘-nitrostilbene (DANS), and 4-di(hydroxy-ethyl)amino-4‘-nitrostilbene (DANS-diol) have been investigated by high-resolution fluorescence excitation and dispersed emission spectroscopy on samples seeded in supersonic expansions. Using ab initio calculations of the harmonic force fields of the electronic ground state as a starting point for the analysis of vibrational modes and frequencies, detailed vibrational assignments of the rich line structure of the S1 ← S0 transition in these three push−pull stilbenes are reported. From the experimental and theoretical analysis, it becomes apparent that the excitation spectra are dominated by low-frequency vibrational modes of the stilbene-like backbone, albeit that a characterization in terms of trans-stilbene vibrational terminology is not very appropriate. The fluorescence excitation and emission spectra show significant Franck−Condon factors for transitions involvin...

The singlet states of the 3p Rydberg manifold of the structurally rigid amines 1-azabicyclo[2.2.2]octane and 1-azaadamantane seeded in supersonic expansions have been investigated by means of fluorescence excitation spectroscopy. Under these conditions a better spectral resolution could be obtained than in previous studies, enabling us to resolve and identify unambiguously the transitions to the second and third excited singlet states. These states are assigned as the 11E and 31A1 states, associated with excitation of a lone-pair electron to the 3px,y and 3pz Rydberg orbitals, respectively. Analysis of the vibrational energies and intensities of vibronic transitions observed in the excitation spectra of both states leads to the conclusion that the equilibrium geometry and vibrational properties of the molecule in these two states resemble closely those of the lowest excited singlet state, which derives from excitation of a lone-pair electron to the 3s Rydberg orbital, and those of their ionic core. Excita...