2015, Marciniak, A., Despré, V., Barillot, T., Rouzée, A., Galbraith, M.C.E., Klei, J., Yang, C.-H., Smeenk, C.T.L., Loriot, V., Nagaprasad Reddy, S., Tielens, A.G.G.M., Mahapatra, S., Kuleff, A.I., Vrakking, M.J.J., Lépine, F.

Highly excited molecular species are at play in the chemistry of interstellar media and are involved in the creation of radiation damage in a biological tissue. Recently developed ultrashort extreme ultraviolet light sources offer the high excitation energies and ultrafast time-resolution required for probing the dynamics of highly excited molecular states on femtosecond (fs) (1 fs=10−15s) and even attosecond (as) (1 as=10−18 s) timescales. Here we show that polycyclic aromatic hydrocarbons (PAHs) undergo ultrafast relaxation on a few tens of femtoseconds timescales, involving an interplay between the electronic and vibrational degrees of freedom. Our work reveals a general property of excited radical PAHs that can help to elucidate the assignment of diffuse interstellar absorption bands in astrochemistry, and provides a benchmark for the manner in which coupled electronic and nuclear dynamics determines reaction pathways in large molecules following extreme ultraviolet excitation.

2015, Barillot, T., Magrakvelidze, M., Loriot, V., Bordas, C., Hervieux, P.-A., Gisselbrecht, M., Johnsson, P., Laksman, J., Mansson, E.P., Sorensen, S., Canton, S.E., Dahlström, J.M., Dixit, G., Madjet, M.E., Lépine, F., Chakraborty, H.S.

We perform time-dependent local density functional calculations of the time delay in C60 HOMO and HOMO-1 photoionization at giant plasmon energies. A semiclassical model is used to develop further insights.