(a) Adiabatic potential energies (green and blue) and nonadiabatic coupling strength divided by 50 (red) for the model potential from Ref. 7. [(b)–(d)] Comparison of the hopping probabilities from state 0 to state 1 using potential (a) and a time step of 2 a.u. obtained from (b) our approach with from Eq. (19), (c) the procedure proposed by Tully (Ref. 7), and (d) the procedure proposed by Tapavicza et al. (Ref. 15).
Theoretical thermally broadened stationary absorption spectrum for the state of trans-BAN obtained from the 300 initial conditions shown in the inset. The discrete absorption lines calculated with the PBE functional were convoluted with a Lorentzian width of 0.04 eV.
Theoretical stationary absorption spectrum for (a) the trans isomer and (b) the cis isomer of BAN obtained using the PBE functional with TZVP basis sets. The calculated discrete transitions energies are convoluted with a Lorentzian width of 0.2 eV. The character of the transition is indicated by the dominant KS orbitals involved in the excitation.
Time-dependent population of the state (red) and of the state of the cis (black, dotted) and trans (black, line dotted) isomers for BAN after excitation of the trans isomer to the state. The lifetime of the state was determined by exponential fitting (dashed red line) giving rise to the value of 219 fs. The structures are classified as cis, if the final dihedral angle was in the range [, ] and as trans, if it was in the range [, ].
Snapshots of the dynamics of BAN for one trajectory exhibiting isomerization to the cis form.
Snapshots of the dynamics of BAN for one trajectory exhibiting no isomerization.
Time-dependent deviation of the normal coordinates of one trajectory isomerizing to the cis form from the equilibrium normal coordinates of trans-BAN. The numbers indicate the corresponding normal modes with respect to increasing frequency.
Calculated TRPES of BAN (a) for the cationic ground state averaged over 220 trajectories and (b) for the ground and eleven excited cationic states obtained from the nonadiabatic dynamics illustrating the population transfer from the to state.
Time-dependent bond length for the (red), (violet) and (blue) bonds of BAN averaged over 220 trajectories.
Article metrics loading...
Full text loading...