A wavelength dependent investigation of the indole photophysics via ionization and fragmentation pump–probe spectroscopies

A wavelength dependent study investigating the low-lying 1La and 1Lb states, both possessing 1ππ* character, and the 1πσ* state in the deactivation process of indole is presented here. Relaxation dynamics following excitation at 241, 250, 260, 270, 273, and 282 nm are examined using three gas-phase, pump–probe spectroscopic techniques: (1) hydrogen atom (H-atom) time-resolved kinetic energy release (TR-KER), (2) time-resolved photoelectron spectroscopy (TR-PES), and (3) time-resolved ion yield (TR-IY). Applied in combination, a more complete picture of the indole relaxation dynamics may be gleaned. For instance, TR-PES experiments directly observe all relaxation pathways by probing the evolution of the excited states following photoexcitation; whereas, TR-KER measurements indirectly, yet specifically, probe for 1πσ*-state activity through the detection of H-atoms eliminated along the indole nitrogen–hydrogen (N–H) stretch coordinate—a possible outcome of 1πσ*-state relaxation in indole. In addition, mass information obtained via TR-IY monitors fragmentation dynamics that may occur within the neutral electronically excited and/or cationic states. The work herein assesses the onset and importance of the 1πσ* state at various pump wavelengths by systematically tuning across the ultraviolet absorption spectrum of indole with a particular focus on those pump wavelengths longer than 263 nm, where the involvement of the 1πσ* state is under current debate. As far as this experimental work is concerned, there does not appear to be any significant involvement by the 1πσ* state in the indole relaxation processes following excitation at 270, 273, or 282 nm. This investigation also evaluates the primary orbital promotions contributing to the 1La, 1Lb, and 1πσ* transitions based on ionization preferences observed in TR-PES spectra. Relaxation time constants associated with dynamics along these states are also reported for excitation at all of the aforementioned pump wavelengths and are used to pinpoint the origin of the discrepancies found in the literature. In this context, advantages and disadvantages of the three experimental techniques are discussed.