Using neon and its dimer as a specific example, it is shown that excited Auger decay channels that are electronically stable in the isolated monomer can relax in a cluster by electron emission. The decay mechanism, leading to the formation of a tricationic cluster, is based on an efficient energy-transfer process from the excited, dicationic monomer to a neighbor. The decay is ultrafast and expected to be relevant to numerous physical phenomena involving core holes in clusters and other forms of spatially extended atomic and molecular matter.
As opposed to purely molecular systems where electron dynamics proceed only through intramolecular processes, weakly bound complexes such as He droplets offer an environment where local excitations can interact with neighbouring embedded molecules leading to new intermolecular relaxation mechanisms. Here, we report on a new decay mechanism leading to the double ionization of alkali dimers attached to He droplets by intermolecular energy transfer. From the electron spectra, the process is similar to the well-known shake-off mechanism observed in double Auger decay and single-photon double ioniz…
We report theory for time-resolved spectator resonant Interparticle Coulombic Decay (ICD) processes. Following excitation by a short extreme ultraviolet pulse, the spectrum of the resonant ICD electron develops. Strong-field ionization is imagined to quench the decay at different time delays and to initiate regular ICD. In this latter process, the ICD electron signal can be measured without interference effects. The typical lifetimes of ICD processes allow for the observation of oscillations of the time- and energy-differential ionization probability. We propose to utilize this oscillation to …
We report the first observation of intermolecular Coulombic decay (ICD) in liquid water following inner-valence ionization. By combining a monochromatized table-top high-harmonic source with a liquid micro-jet, we recorded electron-electron coincidence spectra at two photon energies that identify the ICD electrons, together with the photoelectrons originating from the 2a1 inner-valence band of liquid water. Our results confirm the importance of ICD as a source of low-energy electrons in bulk liquid water and provide quantitative results for modeling the velocity distribution of the slow electr…
We investigate the ionization of HeNe from below the He 1s3p excitation to the He ionization threshold. We observe HeNe$^+$ ions with an enhancement by more than a factor of 60 when the He side couples resonantly to the radiation field. These ions are an experimental proof of a two-center resonant photoionization mechanism predicted by Najjari et al. [Phys. Rev. Lett. 105, 153002 (2010)]. Furthermore, our data provide electronic and vibrational state resolved decay widths of interatomic Coulombic decay (ICD) in HeNe dimers. We find that the ICD lifetime strongly increases with increasing vibra…
To exploit the high intensity of laser radiation, we propose to select frequencies at which single-photon absorption is of too low energy and two or more photons are needed to produce states of an atom that can undergo interatomic Coulombic decay (ICD) with its neighbors. For Ne dimer it is explicitly demonstrated that the proposed scheme to investigate interatomic processes by multiphoton absorption is much more efficient than with single-photon absorption of sufficiently large frequency as used until now. Extensive calculations on Ne dimer including all the involved nuclear dynamics and the …
Photoexcitation of van der Waals complexes can lead to several decay pathways depending on the nature of the potential energy surfaces. Upon excitation of a chromophore in a complex, ionization of its weakly bound neighbour via energy transfer happens via a unique relaxation process known as intermolecular Coulombic decay (ICD); a phenomenon of renewed focus owing to its relevance in biological systems. Herein, we report an experimental evidence of outer-valence ICD induced by multiphoton excitation by near UV radiation of 4.4 eV photons, hitherto unknown in molecular systems. In the binary co…
Relaxation processes following inner-valence ionization of a system can be modified dramatically by embedding this system in a suitable environment. Surprisingly, such an environment can be even composed of helium atoms, the most inert species available. As demonstrated by the examples of Ne and Ca atoms embedded in He droplets, a fast relaxation process [Interatomic Coulombic Decay (ICD)] takes place merely due to the presence of the He surroundings. We have computed ICD widths for both 4He_N and 3He_N droplets doped with Ne and Ca and discuss the findings in some detail. In the case of Ne, I…
Atoms and molecules attached to rare gas clusters are ionized by an interatomic autoionization process traditionally termed 'Penning ionization' when the host cluster is resonantly excited. Here we analyze this process in the light of the interatomic Coulombic decay (ICD) mechanism, which usually contains a contribution from charge exchange at short interatomic distance, and one from virtual photon transfer at large interatomic distance. For helium (He) nanodroplets doped with alkali metal atoms (Li, Rb), we show that long-range and short-range contributions to the interatomic autoionization c…
We investigate the contribution of Interatomic Coulombic Decay induced by ion impact in neon and argon dimers (Ne$_2$ and Ar$_2$) to the production of low energy electrons. Our experiments cover a broad range of perturbation strengths and reaction channels. We use 11.37 MeV/u S$^{14+}$, 0.125 MeV/u He$^{1+}$, 0.1625 MeV/u He$^{1+}$ and 0.150 MeV/u He$^{2+}$ as projectiles and study ionization, single and double electron transfer to the projectile as well as projectile electron loss processes. The application of a COLTRIMS reaction microscope enables us to retrieve the three-dimensional momentu…
Double and triple ionization spectra of isocyanic acid have been measured using multi-electron and ion coincidence techniques combined with synchrotron radiation and compared with high-level theoretical calculations. Vertical double ionization at an energy of 32.8+/-0.3 eV forms the 3A'' ground state in which the HNCO2+ ion is long-lived. The vertical triple ionization energy is determined as 65+/-1 eV. The core-valence double ionization spectra resemble the valence photoelectron spectrum in form, and their main features can be understood on the basis of a simple and rather widely applicable C…
It is shown that differences observed between the ionization potentials of the molecular-doped metallic clusters and those corresponding to the bare metallic ones can be explained by a two-step approach of the classical Liquid Drop Model. This approach takes into account the distinct physical properties of the interface between the molecular core and the metallic shell. Also, it is shown that the presence of the molecular core may act in the determination of the predominant channel of the coulombic fission.
The dynamics of vibrational wave packets excited in Na2 dimers in the triplet ground and excited states is investigated by means of helium nanodroplet isolation (HENDI) combined with femtosecond pump-probe spectroscopy. Different pathways in the employed resonant multi-photon ionization scheme are identified. Within the precision of the method, the wave packet dynamics appears to be unperturbed by the helium droplet environment.
The ionization dynamics of helium droplets in a wide size range from 220 to 10^6 He atoms irradiated with intense femtosecond extreme ultraviolet (XUV) pulses of 10^9 ÷ 10^{12} W/cm2 power density is investigated in detail by photoelectron spectroscopy. Helium droplets are resonantly excited in the photon energy range from ~ 21 eV (corresponding to the atomic 1s2s state) up to the atomic ionization potential (IP) at ~ 25 eV. A complex evolution of the electron spectra as a function of droplet size and XUV intensity is observed, ranging from atomic-like narrow peaks due to binary autoionization…
An ultrafast mechanism belonging to the family of interatomic Coulombic decay (ICD) phenomena is proposed. When two excited species are present, an ultrafast energy transfer can take place bringing one of them to its ground state and ionizing the other one. It is shown that if large homoatomic clusters are exposed to an ultrashort and intense laser pulse whose photon energy is in resonance with an excitation transition of the cluster constituents, the large majority of ions will be produced by this ICD mechanism rather than by two-photon ionization. A related collective-ICD process that is ope…
