Electronic decay through non-linear carbon chains

A multielectron wave-packet propagation method was used to calculate the electronic decay of oxygen and fluorine 2s vacancies for a group of trifluoroalkyl alcohols, HOC_nH_(2n−1)F₃, with n between 1 and 5. Whether ionizing O2s or F2s orbitals, it is shown that an electron can be emitted non-locally from the opposite terminus of the molecule. The decay of the O(2s ⁻¹) state is found to be about 2–3 times faster than that of the F(2s ⁻¹), but in both cases the process takes only a few femtoseconds, demonstrating a highly efficient energy transfer through the carbon bridge. A comparison to the previously reported non-local decay in linear difluorocumulenone systems shows that the non-linearity of the trifluoroalkyl alcohols does not appear to dramatically influence the decay efficiency. These results shed light onto the nature of the scaling of electron correlation and open the door to the potential design of molecules that take advantage of this mechanism. (paper)