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Synchrotron radiation is used to excite Ar to the intermediate states 3p 1/2 5 ͑3dЈ͓3 / 2͔ 1 , 5dЈ͓3 / 2͔ 1 , 5sЈ͓1 / 2͔ 1 , 7sЈ͓1 / 2͔ 1 ͒ and 3p 3/2 5 ͑6d͓1 / 2͔ 1 , 6d͓3 / 2͔ 1 , 8s͓3 / 2͔ 1 ͒, then excited by lasers to the autoionizing Rydberg series 3p 1/2 5 npЈ ͓͑1 / 2͔ 0,1 , ͓3 / 2͔ 1,2 ͒ and nfЈ͓5 / 2͔ 2. For the intermediate states of 5sЈ, 7sЈ, and 8s, the npЈ ͓͑1 / 2͔ 0 and ͓3 / 2͔ 2 ͒ series are observed with high intensity but not the npЈ ͓͑1 / 2͔ 1 and ͓3 / 2͔ 1 ͒ series when the polarization vectors of two light beams are in parallel; but when they are in orthogonal, the npЈ͓1 / 2͔ 0 series disappears, the npЈ͓3 / 2͔ 2 intensity remains, and the npЈ ͓͑1 / 2͔ 1 and ͓3 / 2͔ 1 ͒ series show up strongly. The intensity distribution of the npЈ series strongly depends on the intermediate state. The spectra of the npЈ series are assigned according to their intensity variation with the polarization vectors. The quantum defects determined for the series npЈ͓1 / 2͔ 0 ͑n =11-57͒, npЈ͓3 / 2͔ 2 ͑n =11-65͒, npЈ͓3 / 2͔ 1 ͑n =11-31͒, and nfЈ͓5 / 2͔ 2 ͑n =9-74͒ are 1.611Ϯ 0.011, 1.683Ϯ 0.013, 1.688Ϯ 0.010, and 0.016Ϯ 0.005, respectively. Our values are in excellent agreement with theoretical prediction. The spectral line shapes of autoionizing Rydberg states are analyzed with a Beutler-Fano profile. Reduced autoionization linewidths for the npЈ͓1 / 2͔ 0 ͑n =11-16͒ series vary in the range 2549-4145 cm −1 , and the nfЈ͓5 / 2͔ 2 ͑n =9-11͒ series in 186-247 cm −1 in reasonable agreement with theoretical prediction.

Excited-state intramolecular proton transfer (ESIPT) reaction dynamics in o-hydroxyacetophenone (OHAP) has been investigated in a supersonic molecular beam using femtosecond time-resolved multiphoton ionization mass spectrometry. The observed transients exhibit a biexponential decay and a rapidly damped oscillation with a period of ∼600 fs. The combinations of experimental and theoretical results suggested that the oscillation is due to a coherent vibrational motion that follows the molecular transformation from the initial enol configuration to the final keto form during the ESIPT reaction.