Asymmetric substitution has not been termed as an essential factor in studying photo-induced ultrafast dynamics of molecular system. Asymmetric 4-hydroxybut-3-en-2-one (HEO), together with symmetric malonaldehyde (MA) and acetylacetone (AA), have been provided as target sample to study the nonradiative decay (ND) processes of β-diketones. An effective ND pathway of the three molecules is presented that their excited second (S2) states transfer to first (S1) state by nonadiabatic surface hopping, and then transfer to triplet (T1) state by crossing minimum energy crossing point (MECP), after which decay to ground (S0) state through MECP. More importantly, the asymmetric substitution of HEO induces the proton transfer in the S1 state and generates a proton-transferred conformer with lowest energy, which does not occur for MA and AA. This change exploits a new ND pathway that the S1 state decays to the proton transferred T1 state and then undergoes reverse proton transfer to S0 state through the MECPs between the three states. The two pathways of HEO give detailed energy and geometric information on surface hopping of S2/S1 and MECPs of S1/T1/S0, and interpret the reason of the ND pathway while not spectra emission. This result is significantly different from the previous reported ND pathway of photoisomerization or conical intersection between different states. This work shows that asymmetric substitution changes the molecular structure and then changes their spectra behaviors.
