Electron transfer mediated decay of alkali dimers attached to He nanodroplets.

Alkali metal dimers attached to the surface of helium nanodroplets are found to be efficiently doubly ionized by electron transfer mediated decay (ETMD) when photoionizing the helium droplets. This process is evidenced by detecting in coincidence two energetic ions created by Coulomb explosion and one low-kinetic energy electron. The kinetic energy spectra of ions and electrons are reproduced by simple model calculations based on diatomic potential energy curves, and are in agreement with ab initio calculations for the He-Na2 and He-KRb systems. This work demonstrates that ETMD is an important decay channel in heterogeneous nanosystems exposed to ionizing radiation.

Enhanced Ionization of Embedded Clusters by Electron-Transfer-Mediated Decay in Helium Nanodroplets.

We report the observation of electron-transfer-mediated decay (ETMD) involving magnesium (Mg) clusters embedded in helium (He) nanodroplets. ETMD is initiated by the ionization of He followed by removal of two electrons from the Mg clusters of which one is transferred to the He ion while the other electron is emitted into the continuum. The process is shown to be the dominant ionization mechanism for embedded clusters for photon energies above the ionization potential of He. For Mg clusters larger than five atoms we observe stable doubly ionized clusters. Thus, ETMD provides an efficient pathway to the formation of doubly ionized cold species in doped nanodroplets.

X-Ray absorption spectra of microsolvated metal cations.

Core excited states in clusters or bulk medium are known to undergo a process of internal ionisation, whereby the excited electron delocalises throughout the medium. This delocalisation is visible in the shifting and broadening of lines in X-ray absorption spectra, and it impacts the electronic decay initiated by photoabsorption. In this paper we study the delocalisation of electrons excited from the 1s core orbital of Na(+) and Mg(2+) ions in microsolvated Na(+)(H2O)m and Mg(2+)(H2O)m clusters (m = 1-6) by computing the X-ray absorption spectra and electron distributions in different core excited states. We show that addition of water ligands to the ion leads to more and more pronounced delocalisation of the core-to-valence 1s → 3p and core-to-Rydberg 1s → 4p excitations. Even for the compact 1s → 3p excitation the excited electron is mostly located on the water molecules when the solvation shell is complete. We also found that the degree of delocalisation strongly depends on the cluster geometry and the ionic charge. These results indicate that even in small microsolvated clusters delocalisation of core excited electrons is substantial and will affect the following electronic decay. The accuracy and transferability of our results are corroborated by the good agreement between our XAS spectra of microsolvated Na(+) and experimental X-ray absorption spectra of dilute NaCl solutions.

Impact of metal ion's charge on the interatomic Coulombic decay widths in microsolvated clusters.

Interatomic Coulombic decay (ICD) is an efficient electronic decay mechanism of electronically excited atoms and molecules embedded in an environment. For the series of isoelectronic Na(+), Mg(2+), and Al(3+) ions in aqueous solution, ultrashort ICD lifetimes of 3.1 fs, 1.5 fs, and 0.9 fs, respectively, were observed experimentally. The magnitude of the ICD lifetimes and their variation within the series were qualitatively explained by shortening metal-oxygen equilibrium distances and the increasing polarization of the water molecules as the metal's charge grows. We carried out an extensive ab initio investigation of the variation of the ICD widths with the metal-oxygen distances and the number of water neighbors in Na(+)-(H2O)m (m = 1-4) and Mg(2+)-(H2O)n (n = 1-6) clusters including and excluding polarization effects in the decaying state. We demonstrated that the effect of the induced polarization of the water ligand and the equilibrium cation-oxygen distance are equally important in determining the ordering and ratios of the ICD lifetimes in the series. Moreover, we showed that the induced polarization of the water molecules leads to a slower than linear growth of ICD width with the number of equivalent water neighbors; the non-linearity is stronger for Mg(2+). The ab initio ICD widths in microsolvated Na(+)-(H2O)4 and Mg(2+)-(H2O)6 clusters are found to be in good agreement with the experimental values.

Enhanced one-photon double ionization of atoms and molecules in an environment of different species.

The correlated nature of electronic states in atoms and molecules is manifested in the simultaneous emission of two electrons after absorption of a single photon close to the respective threshold. Numerous observations in atoms and small molecules demonstrate that the double ionization efficiency close to threshold is rather small. In this Letter we show that this efficiency can be dramatically enhanced in the environment. To be specific, we concentrate on the case where the species in question has one or several He atoms as neighbors. The enhancement is achieved by an indirect process, where a He atom of the environment absorbs a photon and the resulting He(+) cation is neutralized fast by a process known as electron transfer mediated decay, producing thereby doubly ionized species. The enhancement of the double ionization is demonstrated in detail for the example of the Mg · He cluster. We show that the double ionization cross section of Mg becomes 3 orders of magnitude larger than the respective cross section of the isolated Mg atom. The impact of more neighbors is discussed and the extension to other species and environments is addressed.

The effect of the partner atom on the spectra of interatomic Coulombic decay triggered by resonant Auger processes.

The resonant-Auger - interatomic Coulombic decay (ICD) cascade was recently suggested as an efficient means of controlling the course of the ICD process. Recent theoretical and experimental works show that control over the energies of the emitted ICD electrons can be achieved either by varying the photon energy to produce different initial core excitations or by changing the neighboring species. This work presents a theoretical investigation on the role of the rare-gas neighbor and clarifies how the latter influences the ICD process. For this purpose, we compare fully ab initio computed ICD-electron and kinetic energy release spectra following the 2p(3/2) → 4s, 2p(1/2) → 4s and 2p(3/2) → 3d of Ar in ArKr and Ar2. We demonstrate that the presence of the chemically "softer" partner atom results in an increase in the energies of the emitted ICD electrons, and also in the appearance of additional ICD-active states. The latter leads to a threefold increase in the ICD yield for the case of the 2p(3/2, 1/2) → 4s parent core excitations.

Interatomic Coulombic decay following resonant core excitation of Ar in argon dimer.

A scheme utilizing excitation of core electrons followed by the resonant-Auger - interatomic Coulombic decay (RA-ICD) cascade was recently proposed as a means of controlling the generation site and energies of slow ICD electrons. This control mechanism was verified in a series of experiments in rare gas dimers. In this article, we present fully ab initio computed ICD electron and kinetic energy release spectra produced following 2p(3/2) → 4s, 2p(1/2) → 4s, and 2p(3/2) → 3d core excitations of Ar in Ar2. We demonstrate that the manifold of ICD states populated in the resonant Auger process comprises two groups. One consists of lower energy ionization satellites characterized by fast interatomic decay, while the other consists of slow decaying higher energy ionization satellites. We show that accurate description of nuclear dynamics in the latter ICD states is crucial for obtaining theoretical electron and kinetic energy release spectra in good agreement with the experiment.

Ab initio calculation of ICD widths in photoexcited HeNe.

Excitation of HeNe by synchrotron light just below the frequency of the 1s → 3p transition of isolated He has been recently shown to be followed by resonant interatomic Coulombic decay (ICD). The vibrationally resolved widths of the ICD states were extracted with high precision from the photoion spectra. In this paper, we report the results of ab initio calculations of these widths. We show that interaction between electronic states at about the equilibrium distance of HeNe makes dark states of He accessible for the photoexcitation and subsequent electronic decay. Moreover, the values of the calculated widths are shown to be strongly sensitive to the presence of the non-adiabatic coupling between the electronic states participating in the decay. Therefore, only by considering the complete manifold of interacting decaying electronic states a good agreement between the measured and computed ICD widths can be achieved.

Total photoionization cross-sections of excited electronic states by the algebraic diagrammatic construction-Stieltjes-Lanczos method.

Here, we extend the L2 ab initio method for molecular photoionization cross-sections introduced in Gokhberg et al. [J. Chem. Phys. 130, 064104 (2009)] and benchmarked in Ruberti et al. [J. Chem. Phys. 139, 144107 (2013)] to the calculation of total photoionization cross-sections of molecules in electronically excited states. The method is based on the ab initio description of molecular electronic states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. The intermediate state representation of the dipole operator in the ADC basis is used to compute the transition moments between the excited states of the molecule. We compare the results obtained using different levels of the many-body theory, i.e., ADC(1), ADC(2), and ADC(2)x for the first two excited states of CO, N2, and H2O both at the ground state and the excited state equilibrium or saddle point geometries. We find that the single excitation ADC(1) method is not adequate even at the qualitative level and that the inclusion of double electronic excitations for description of excited state photoionization is essential. Moreover, we show that the use of the extended ADC(2)x method leads to a substantial systematic difference from the strictly second-order ADC(2). Our calculations demonstrate that a theoretical modelling of photoionization of excited states requires an intrinsically double excitation theory with respect to the ground state and cannot be achieved by the standard single excitation methods with the ground state as a reference.

Efficient pathway to neutralization of multiply charged ions produced in Auger processes.

After core ionization of an atom or molecule by an x-ray photon, multiply charged ions are produced in the Auger decay process. These ions tend to neutralize their charge when embedded in an environment. We demonstrate that, depending on the atom or molecule and its neighbors, electron transfer mediated decay (ETMD) provides a particularly efficient neutralization pathway for the majority of the ions produced by Auger decay. The mechanism is rather general. As a showcase example, we conducted an ab initio study of the NeKr2 cluster after core ionization of the Ne atom. This example has been chosen because it is amenable to both ab initio calculations and coincidence experiments. We find that even for frozen nuclei, the neutralization rate can be as fast as 0.130 ps(-1). We also show that nuclear dynamics may increase the rate by about an order of magnitude. The generality of the mechanism makes this neutralization pathway important in weakly bonded environments.

Vibrationally resolved decay width of interatomic Coulombic decay in HeNe.

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 in HeNe dimers. We find that the interatomic Coulombic decay lifetime strongly increases with increasing vibrational state.

Total molecular photoionization cross-sections by algebraic diagrammatic construction-Stieltjes-Lanczos method: benchmark calculations.

In [K. Gokhberg, V. Vysotskiy, L. S. Cederbaum, L. Storchi, F. Tarantelli, and V. Averbukh, J. Chem. Phys. 130, 064104 (2009)] we introduced a new L(2) ab initio method for the calculation of total molecular photoionization cross-sections. The method is based on the ab initio description of discretized photoionized molecular states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. Here we establish the accuracy of the new technique by comparing the ADC-Lanczos-Stieltjes cross-sections in the valence ionization region to the experimental ones for a series of eight molecules of first row elements: HF, NH3, H2O, CO2, H2CO, CH4, C2H2, and C2H4. We find that the use of the second-order ADC technique [ADC(2)] that includes double electronic excitations leads to a substantial systematic improvement over the first-order method [ADC(1)] and to a good agreement with experiment for photon energies below 80 eV. The use of extended second-order ADC theory [ADC(2)x] leads to a smaller further improvement. Above 80 eV photon energy all three methods lead to significant deviations from the experimental values which we attribute to the use of Gaussian single-electron bases. Our calculations show that the ADC(2)-Lanczos-Stieltjes technique is a reliable and efficient ab initio tool for theoretical prediction of total molecular photo-ionization cross-sections in the valence region.

Quenching molecular photodissociation by intermolecular Coulombic decay.

In this paper we study the impact of interatomic Coulombic decay (ICD) on molecular photodissociation. The investigation reveals the hitherto unrecognized ability of ICD to quench processes involving nuclear rearrangements. Numerical computations of the nuclear dynamics, initiated by photoexciting the B(1)Σ(+) Rydberg state of CO in CO·Mg complexes, are carried out. The efficiencies of ICD and photoinduced predissociation are compared for the four lowest vibrational levels of the corresponding electronic state. We also show the impact of CO vibrations on the ICD electron spectrum. Finally, we discuss the growing efficiency of ICD to quench the dissociation as the number of neighboring Mg atoms is increased.

Ultrafast temporal evolution of interatomic Coulombic decay in NeKr dimers.

We investigate interatomic Coulombic decay in NeKr dimers after neon inner-valence photoionization [Ne+(2s-1)] using a synchrotron light source. We measure with high energy resolution the two singly charged ions of the Coulomb-exploding dimer dication and the photoelectron in coincidence. By carefully tracing the post-collision interaction between the photoelectron and the emitted ICD electron we are able to probe the temporal evolution of the state as it decays. Although the ionizing light pulses are 80 picoseconds long, we determine the lifetime of the intermediate dimer cation state and visualize the contraction of the nuclear structure on the femtosecond time scale.

Ab initio interatomic decay widths of excited states by applying Stieltjes imaging to Lanczos pseudospectra.

Electronically excited states of atoms and molecules in an environment may decay in interatomic processes by transferring excess energy to neighboring species and ionizing them. The corresponding interatomic decay width is the most important characteristic of the decay allowing to calculate its efficiency and the final states' distribution. In this paper we present calculations of interatomic widths by the Fano-Stieltjes method applied to Lanczos pseudospectra, which has been previously shown to provide accurate autoionization widths in atoms and molecules. The use of Lanczos pseudospectra allows one to avoid the full diagonalization bottleneck and makes the method applicable to larger systems. We apply the present method to the calculation of interatomic decay widths in NeMg, NeAr and HCN[middle dot]Mg(n), n = 1, 2 clusters. The results are compared with widths obtained analytically and by other ab initio methods where available.

Autoionization widths by Stieltjes imaging applied to Lanczos pseudospectra.

Excited states of atoms and molecules lying above the ionization threshold can decay by electron emission in a process commonly known as autoionization. The autoionization widths can be calculated conveniently using Fano formalism and discretized atomic and molecular spectra by a standard procedure referred to as Stieltjes imaging. The Stieltjes imaging procedure requires the use of the full discretized spectrum of the final states of the autoionization, making its use for poly-atomic systems described by high-quality basis sets impractical. Following our previous work on photoionization cross-sections, here we show that also in the case of autoionization widths, the full diagonalization bottleneck can be overcome by the use of Lanczos pseudospectra. We test the proposed method by calculating the well-documented autoionization widths of inner-valence-excited neon and apply the new technique to autoionizing states of hydrofluoric acid and benzene.

Calculation of resonant interatomic Coulombic decay widths of inner-valence-excited states delocalized due to inversion symmetry.

Inner-valence-excited states of clusters can decay by electron emission via several of mechanisms, the leading ones being intra-atomic autoionization and resonant interatomic Coulombic decay. Recently, we have derived the Wigner-Weisskopf theory for the calculation of the decay widths of the inner-valence excitations [J. Chem. Phys. 124, 144315 (2006)]. While the new method has been successful in producing the decay rates of heteronuclear diatomic clusters, it cannot be applied to systems possessing inversion symmetry, e.g., to homonuclear diatoms, due to delocalization of the molecular orbitals involved in the decay processes. In the present work, we show that the Wigner-Weisskopf theory of the decay of inner-valence-excited states can be generalized to systems with inversion symmetry using a technique of adapted final states [J. Chem. Phys. 125, 094107 (2006)]. The same technique can be employed when going beyond the Wigner-Weisskopf theory. We consider the experimentally relevant case of competing resonant interatomic Coulombic decay and autoionization in neon dimer and calculate the rates of these processes for a series of inner-valence-excited states which has been measured by Aoto et al. [Phys. Rev. Lett. 97, 243401 (2006)].

Molecular photoionization cross sections by Stieltjes-Chebyshev moment theory applied to Lanczos pseudospectra.

Stieltjes imaging technique is widely used for the ab initio computation of photoionization cross sections and decay widths. The main problem hampering the application of the standard Stieltjes imaging algorithms in conjunction with high-level ab initio methods to polyatomic molecules is the requirement of full diagonalization of excessively large Hamiltonian matrices. Here we show that the full diagonalization bottleneck can be overcome by applying the Stieltjes imaging procedure to Lanczos pseudospectrum of the atomic or molecular Hamiltonian. Using the helium and neon atoms as examples, we demonstrate that the Lanczos pseudospectrum obtained after only a relatively small number of iterations can be used for Stieltjes-type calculations of photoionization cross sections essentially without loss of accuracy. The new technique is applied to the calculation of the total photoionization cross section of benzene within an ab initio approach explicitly taking into account single and double electronic excitations. Good agreement with experimental results is obtained.

Charge transfer to ground-state ions produces free electrons.

Inner-shell ionization of an isolated atom typically leads to Auger decay. In an environment, for example, a liquid or a van der Waals bonded system, this process will be modified, and becomes part of a complex cascade of relaxation steps. Understanding these steps is important, as they determine the production of slow electrons and singly charged radicals, the most abundant products in radiation chemistry. In this communication, we present experimental evidence for a so-far unobserved, but potentially very important step in such relaxation cascades: Multiply charged ionic states after Auger decay may partially be neutralized by electron transfer, simultaneously evoking the creation of a low-energy free electron (electron transfer-mediated decay). This process is effective even after Auger decay into the dicationic ground state. In our experiment, we observe the decay of Ne2+ produced after Ne 1s photoionization in Ne-Kr mixed clusters.

The role of metal ions in X-ray-induced photochemistry.

Metal centres in biomolecules are recognized as being particularly sensitive to radiation damage by X-ray photons. This results in such molecules being both susceptible to an effective X-ray-induced loss of function and problematic to study using X-ray diffraction methods, with reliable structures of the metal centres difficult to obtain. Despite the abundance of experimental evidence, the mechanistic details of radiation damage at metal centres are unclear. Here, using ab initio calculations, we show that the absorption of X-rays by microsolvated Mg(2+) results in a complicated chain of ultrafast electronic relaxation steps that comprise both intra- and intermolecular processes and last for a few hundred femtoseconds. At the end of this cascade the metal reverts to its original charge state, the immediate environment becomes multiply ionized and large concentrations of radicals and slow electrons build up in the metal's vicinity. We conclude that such cascades involving metal ions are essential to our understanding of radiation chemistry and radiation damage in biological environments.