Electronic decay following ionization of aqueous Li+ microsolvation clusters

Müller, Imke; Cederbaum, Lorenz S.

doi:10.1063/1.1854118

Cited by 46 publications

(39 citation statements)

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“…For example, the interaction matrices of the tetracationic decaying states are essentially spanned by the large 3h1p block, making a full ab initio computation of decay widths unfeasible for bigger systems. However, as was demonstrated in previous studies on ETMD and ICD, a good approximation to the electronic decay widths can be obtained by adding up decay widths calculated for subunits of a system [7,8]. The approximation can be exemplified for the total ICD width in a cluster with N water neighbours:…”

Section: Determination Of the Widths Of Electronic Decaymentioning

confidence: 99%

“…The energies of pentacationic states were obtained by multi-reference configuration interaction method including single and double excitations (DIRECT-CI) [45] implemented in the GAMESS-UK 8.0 quantum chemistry package [46] The total and partial electronic decay widths were calculated by means of Fano-ADCStieltjes method [16,47]. Due to numerical limitations, the decay widths for the Mg 4+ (H 2 O) 6 states were determined in an additive approximation [48,49]. For details of this approximation and calculation of the partial decay widths see the Supplementary information.…”

Section: Methodsmentioning

confidence: 99%

“…The metal ion may become oxidised, reduced or even remain unaltered [5,6]; the particular outcome depends on the initial metal charge and the nature of ligands. Ample evidence from a different field, that of the X-ray crystallography, demonstrates that the radiation damage inflicted on a sample is highly non-random [7]. Importantly, in metallo-proteins the site containing the metal is one of the weak spots; it is often damaged at a dose much lower than the one at which the rest of the protein molecule is damaged [8].…”

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confidence: 99%

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

2016

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Metal ions play numerous important roles in biological systems being central to the function of biomolecules. In this letter we show that the absorption of X-rays by these ions leads to a complicated chain of ultrafast relaxation steps resulting in the complete degradation of their nearest environment. We conducted high quality ab initio studies on microsolvated Mg 2+ clusters demonstrating that ionisation of an 1s-electron of Mg leads to a complicated electronic cascade comprising both intra-and intermolecular steps and lasting only a few hundreds femtoseconds.The metal cation reverts to its original charge state at the end of the cascade, while the nearest solvation shell becomes multiply ionised and large concentrations of radical and slow electron species build up in the metal's vicinity. We conclude that such cascades involving metal ions are essential for understanding the radiation chemistry of solutions and radiation damage to metal containing biomolecules.

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Section: Determination Of the Widths Of Electronic Decaymentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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

2016

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“…[10][11] In recent years a set of novel non-local autoionization processes has been identified to play an important role in weakly bonded atomic and molecular systems. [12][13][14] One such relaxation process is Intermolecular Coulombic Decay (ICD), initially observed upon innervalence ionization of van der Waals-bonded clusters, 12,[15][16][17] and later also (hydrogen bonded) water clusters. 18 In the ICD process, the energy provided by an outer valence electron upon filling the vacancy is used to expel a second electron from an atom or molecule neighboring the initially ionized site.…”

Section: Identifying the Initial Products Of The Interaction Of High-mentioning

confidence: 99%

“…Figure 3a) Figure S4). Inset: Kinetic energies of electrons originating from local 13 Auger process for light and heavy water for two different times; the position of all peaks was shifted to match the experimental maximum of the local Auger peak of normal water.…”

Section: Figurementioning

confidence: 99%

On the nature and origin of dicationic, charge-separated species formed in liquid water on X-ray irradiation

et al. 2013

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Identifying the initial products of the interaction of high-energy radiation with liquidwater is essential for understanding the yield and patterns of damage in aqueous condensed matter, including biological systems. Up until now several fast reactions induced by energetic particles in water could not be observed on their characteristic timescales, and hence some of the reaction intermediates involved, particularly those requiring nuclear motion, have not been considered in describing radiation chemistry.Here, through a combined experimental and theoretical study, we elucidate the ultrafast proton dynamics in the first few femtoseconds after X-ray core-level ionization of liquid water. We show through isotope analysis of the Auger-spectra that proton-transfer dynamics occurs on the same timescale as electron autoionization. Proton transfer leads to formation of a Zundel-type intermediate [HO*··H··OH 2 ] + , which further ionizes, forming a so-far unnoticed type of di-cationic, charge-separated species with high internal energy. We call the process proton-transfer mediated charge separation.The primary processes in water initiated by X-radiation are poorly understood despite their paramount importance in different fields. Understanding the energy and charge redistribution in water upon X-ray photon absorption is vital for a design of more efficient radio-oncology schemes, 1-2 for disentangling the physical basis of genotoxic effects on living tissues, [3][4][5] for minimizing the damage of biological samples during X-ray diffraction 2 experiments, 6 as well as for controlling the performance of nuclear reactors under operating conditions. 7 Current understanding of electron-initiated processes in aqueous systems, following energy deposition, and the subsequent radical chemistry have been recently reviewed. 8 An explicit consideration of radicals and molecular species formed via multiple ionization processes of water, involving for instance atomic oxygen and hydrogen peroxide, can be found in the radiolysis literature, e.g. in refs. 7,9 However, the knowledge of the ultrafast processes and mechanisms in water radiolysis remains to large extent unexplored.In the present work we focus on the processes following O1s core-level ionization of water. The highly excited species formed by the core ionization relaxes primarily via Augerelectron decay. As shown in Figure 1b, Auger decay of a water molecule involves refilling the water core-hole by one of the valence electrons, and the simultaneous emission of another valence electron, the Auger electron, from the same water molecule. The resulting highly reactive doubly ionized H 2 O 2+ (aq) molecule, with both vacancies (holes) located at the same site (denoted here as 2h state), then undergoes ultrafast Coulomb explosion, forming dominantly O + 2H + . [10][11] In recent years a set of novel non-local autoionization processes has been identified to play an important role in weakly bonded atomic and molecular systems. [12][13][14] One such relaxation process is Intermolecu...

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Effect of Protonation and Deprotonation on Electron Transfer Mediated Decay and Interatomic Coulombic Decay

Kumar

Vaval

2022

ChemPhysChem

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Electronically excited atoms or molecules in an environment are often subject to interatomic/intermolecular Coulombic decay (ICD) and/or electron transfer mediated decay (ETMD) mechanisms. Various factors like, for instance, bond distance, number of surrounding atoms or molecules, and polarization effect affect these non-radiative decay mechanisms. In this paper, we have studied the effect of protonation and deprotonation on the ionization potential (IP), double ionization potential (DIP), and lifetimes (or decay width) of temporary bound states in these non-radiative decay processes. We have chosen LiH-NH 3 and LiH-H 2 O as test systems. The equation of motion coupled cluster singles and doubles method augmented by a complex absorbing potential (CAP-EOM-CCSD) is used to calculate the energetic position of the decaying states and the system's decay rate. After ionization of the shallow core of Li and inner valence ionization of H 2 O and NH 3 , our analysis reveals that the deprotonation lowers the IP and DIP compared to the respective neutral systems. In contrast, protonation increases these quantities compared to the neutral systems. The lowering of the DIP due to deprotonation opens the decay channels, whereas protonation closes the relaxation channels for ICD/ETMD. Our study shows that the efficiency, i.e., the rate of ICD/ETMD, can be altered by protonation

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Electronic decay following ionization of aqueous Li+ microsolvation clusters

Cited by 46 publications

References 40 publications

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

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

On the nature and origin of dicationic, charge-separated species formed in liquid water on X-ray irradiation

Effect of Protonation and Deprotonation on Electron Transfer Mediated Decay and Interatomic Coulombic Decay

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