Rydberg states: sensitive probes of molecular structure

Time-dependent photoionization of azulene: Optically induced anistropy on the femtosecond scale

“…This doubly excited state has been detected by magnetic circular dichroism on different derivatives of azulene around 4.95 eV. (29) The photoelectron images show the fingerprint of the Rydberg states, (30,31) which is manifest by the observation that the photoelectron spectrum is invariant to the pump wavelength. (7) The characteristic spectrum is depicted on the right hand side of Fig.…”

Atmospheric photochemical loss of H and H2from formaldehyde: the relevance of ultrafast processes

“…What is noteworthy about this observation is that Rydberg potential energy surfaces generally have the same shape along a given coordinate. 18,19 The reason for this is that the ionic core of the Rydberg-excited species determines the shape of the potential energy surface (the Rydberg electron is too far away from the nuclei to influence the energy). 19 In this case the Rydberg states are the exception to the rule, one possible explanation could be that the Rydberg orbitals pointing in the direction of the CQO group are significantly polarized.…”

Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States

“…While historically static structure determination methods, such as electron diffraction, have been adapted to fast time scales, there are some limitations, for example, relating to the size of the molecular system [10][11][12][13][14]. Rydberg fingerprint spectroscopy (RFS) takes advantage of the fact that the binding energies of electrons in Rydberg states are sensitive towards the arrangement of atoms in the ion core [15][16][17][18][19]. Because the structure in a Rydberg state most often closely resembles that of the ion state, the spectra of these states feature sharp peaks without vibrational broadening [20][21][22].…”