Ionization and double ionization of small water clusters

Müller, Imke; Cederbaum, Lorenz S.

doi:10.1063/1.2357921

Cited by 90 publications

(85 citation statements)

References 52 publications

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“…A KER of 4.9 eV corresponds to R = 2.9 Å. This value nicely corresponds to typical distances of the two molecules of the water dimer in its ground state 21 as shown by the red oval in Fig. 1a.…”

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confidence: 70%

“…This has the advantage that all charged particles that are created during the process can be measured in coincidence and in addition the system is small enough to allow for theoretical modelling of all steps of the process in the future. Model calculations for the primary ICD step in water dimers for a fixed geometry have already been reported 21 . We trigger the process by removing an inner-valence electron from one of the water molecules of the dimer.…”

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confidence: 99%

“…4 (top), adapted from ref. 21) shows that the distribution from approximately 4 to 13 eV corresponds to a photoelectron leaving the singly charged water dimer ion in a single inner-valance hole state. These photoelectrons are accompanied by a second, low-energy electron from the ICD.…”

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Ultrafast energy transfer between water molecules

et al. 2010

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At the transition from the gas to the liquid phase of water, a wealth of new phenomena emerge, which are absent for isolated H 2 O molecules. Many of those are important for the existence of life, for astrophysics and atmospheric science. In particular, the response to electronic excitation changes completely as more degrees of freedom become available. Here we report the direct observation of an ultrafast transfer of energy across the hydrogen bridge in (H 2 O) 2 (a so-called water dimer). This intermolecular coulombic decay leads to an ejection of a low-energy electron from the molecular neighbour of the initially excited molecule. We observe that this decay is faster than the proton transfer that is usually a prominent pathway in the case of electronic excitation of small water clusters and leads to dissociation of the water dimer into two H 2 O , the observed decay channel might contribute as a source of electrons that can cause radiation damage in biological matter.The water molecule is, as a triatomic molecule, rather simple in structure and its geometry is well known. In contrast to that, the interplay of compounds of water molecules or other atoms and molecules with water, for example in a solution, is very rich and far from being fully understood. At the very onset of condensation when two water molecules are combined to form a water dimer a new dimension of complexity arises: electronic excitation of this complex spawns nuclear dynamics leading to fragmentation into a protonated fragment (that is, H 3 O + ) and an OH group 3,4 . For this fragmentation, first a proton migrates from one of the molecules to its neighbour, usually along a distance that is larger than the bond lengths found in the water molecule itself. Such fragmentation dynamics are characteristic for larger clusters, as well 5 . Typical mass spectra of fragments of water droplets show a break-up into protonated cluster fragments (H 2 O) n H + of different sizes and into OH groups. A reason for this is the absence of direct transitions within the Franck-Condon region to break-up channels that do not involve proton migration [6][7][8] . Furthermore, the migration itself is highly efficient and occurs on a timescale of <60 fs (ref. 9).The response of condensed water to electronic excitation has far-reaching consequences for biological systems. Radiation damage to cells naturally depends sensitively on the routes by which energy deposited into the cells is finally distributed and which fragmentation and de-excitation pathways are favoured. Experiments have shown that the constituents of DNA are highly vulnerable to low-energy electrons 1 . These studies revealed that not only does primary ionization by high-energy particles or photons cause damage, but also that low-energy electrons in particular break-up biomolecules efficiently 2 . ). The red oval shows an internuclear distance of 2.9 Å with a corresponding KER of 4.9 eV after the photo reaction. b,c, The process observed in this experiment: an electron from the inner valence shell of one...

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Ultrafast energy transfer between water molecules

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“…These properties of ICD and the fact that it appeared to be ubiquitious in hydrogenbonded systems [6][7][8] suggest its potential importance for radiation damage [9]. Low-energy electrons (LEEs) [10,11], as well as radical cations [12], the direct products of the ICD, are known to be effective in causing single-and double-strand breaks in DNA.…”

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Site- and energy-selective slow-electron production through intermolecular Coulombic decay

Gokhberg

Kolorenč

Kuleff

et al. 2013

Nature

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140

133

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Since its discovery in 1997 [1], the ICD has been successfully investigated in a variety of systems [2]. It usually proceeds on a femtosecond timescale and becomes faster the more neighbors are present, dominating most of the competing relaxation processes. Experimental investigation of ICD in water dimers [3] found the rate of this process to be so large as to completely suppress the proton transfer in the inner-valence ionized water molecules.As a result of ICD, two intact water cations are produced by the consecutive Coulomb 1

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“…One case of particular importance is the MCPI simulation of liquid water and water clusters. 30,[48][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] In our recent work 24 on water clusters we constrain all the intramolecular DF. It is not obvious that the resulting simulation should yield satisfactory results at temperatures above 250 K, where excitation of the bending degree of freedom may have a detectable effect on sensitive thermodynamic properties.…”

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A stereographic projection path integral study of the coupling between the orientation and the bending degrees of freedom of water

Curotto

Freeman

Doll

2008

The Journal of Chemical Physics

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A Monte Carlo path integral method to study the coupling between the rotation and bending degrees of freedom for water is developed. It is demonstrated that soft internal degrees of freedom that are not stretching in nature can be mapped with stereographic projection coordinates. For water, the bending coordinate is orthogonal to the stereographic projection coordinates used to map its orientation. Methods are developed to compute the classical and quantum Jacobian terms so that the proper infinitely stiff spring constant limit is recovered in the classical limit, and so that the nonconstant nature of the Riemann Cartan curvature scalar is properly accounted in the quantum simulations. The theory is used to investigate the effects of the geometric coupling between the bending and the rotating degrees of freedom for the water monomer in an external field in the 250 to 500 K range. We detect no evidence of geometric coupling between the bending degree of freedom and the orientations.

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Ionization and double ionization of small water clusters

Cited by 90 publications

References 52 publications

Ultrafast energy transfer between water molecules

Ultrafast energy transfer between water molecules

Site- and energy-selective slow-electron production through intermolecular Coulombic decay

A stereographic projection path integral study of the coupling between the orientation and the bending degrees of freedom of water

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