Dynamics of H-atom loss in adenine

Gas-Phase IR Spectroscopy of Nucleobases

“…For 4-aminopyrimidine, surface hopping calculations identified two conical intersections (5,33,(80)(81)(82)(83)(84)(85)(86)(87)(88)(89)(90)(91)(92): deformation at the C2 position leads to deactivation of the excited state with a lifetime, τ*, of 1 ps and deformation at the C5=C6 bond with a τ* of 400 fs. Immobilizing the latter with a 5 membered ring forms adenine with a conical intersection due to the C2 deformation, τ* of 1 ps and dynamics similar to that in guanine.…”

Time‐Resolved Photoelectron Spectroscopy of Nonadiabatic Dynamics in Polyatomic Molecules

“…By contrast, the first TRPES studies compared adenine electronic relaxation dynamics at two different wavelengths, 266 nm vs. 250 nm, and concluded that the πσ * state may indeed be important [189,190]. Additional evidence of πσ * state participation obtained from H-atom loss experiments [191,192]. Hydrogen atom detection is highly sensitive and can reveal even minor H-atom loss channels.…”

On the Participation of Photoinduced N–H Bond Fission in Aqueous Adenine at 266 and 220 nm: A Combined Ultrafast Transient Electronic and Vibrational Absorption Spectroscopy Study

“…[36][37][38][39] With specific regard to the participation of the 1 πσ* state in 9H-Ade's photochemistry, a number of studies have been performed to investigate the activity of this channel. [38][39][40][41][42][43][44] Early work in both the time and frequency domains led a number of research groups to infer that ultrafast relaxation via this state may in fact be active following excitation at 267 nm; 38, 41, 42 a much longer wavelength than initially predicted by Domcke and co-workers 14 and later theoretical work. 18,21 However, high-resolution photofragment translational spectroscopy measurements by Nix et al.…”