Electronic Spectroscopy and Ultrafast Energy Relaxation Pathways in the lowest Rydberg States of Trimethylamine

摘要

Resonance-enhanced multiphoton ionization photoelectron spectroscopy has been applied to study the electronic spectroscopy and relaxation pathways amongst the 3p and 3s Rydberg states of trimethylamine. The experiments used femtosecond and picosecond duration laser pulses at wavelengths of 416 nm, 266 nm, and 208 nm, and employed two-photon and three-photon ionization schemes. The binding energy of the 3s Rydberg state was found to be 3.087 ± 0.005 eV. The degenerate 3px,y states have binding energies of 2.251 ± 0.005 eV, and 3pz is at 2.204 ± 0.005 eV. Using picosecond and femtosecond time-resolved experiments we spectrally and temporally resolved an intricate sequence of energy relaxation pathways leading from the 3p states to the 3s state. With excitation at 5.96 eV, trimethylamine is found to decay from the 3pz state to 3px,y in 539 fs. The decay to 3s from all the 3p states takes place with a 2.9 ps time constant. On these time scales, trimethylamine does not fragment at the given internal energies, which range from 0.42 to 1.54 eV depending on the excitation wavelength and the electronic state.