Nuclear quantum effects in the direct ionization process of pure helium clusters; Path-integral and ring-polymer molecular dynamics simulations on the diatomics-in-molecule potential energy surfaces

Suzuki, Kento*; Miyazaki, Takaaki*; Takayanagi, Toshiyuki*; Shiga, Motoyuki

Physical Chemistry Chemical Physics, 20(41), p.26489 - 26499, 2018/11

https://doi.org/10.1039/C8CP05389H

The direct photoionization of pure helium clusters and its subsequent short-time process have been studied by path integral molecular dynamics (PIMD) and ring-polymer molecular dynamics (RPMD) simulations. The PIMD simulations reproduced the experimental ionization spectra with a broad and asymmetric nature, which can be ascribed to the inhomogeneity of the energy levels of He atoms. From the RPMD simulations, it is found that the ionized helium cluster in the highly excited state brings about fast electronic state relaxation via nonadiabatic charge transfer and subsequently slow structural relaxation.