@article{NasdalaWildnerWirthetal.2006, author = {Nasdala, Lutz and Wildner, Manfred and Wirth, Richard and Groschopf, Nora and Pal, Dipak C. and M{\"o}ller, Andreas}, title = {Alpha particle haloes in chlorite and cordierite}, year = {2006}, abstract = {Effects of the impact of natural long-term irradiation with alpha particles in one chamosite and one cordierite sample were characterised in detail using electron microprobe, Raman microprobe, optical absorption spectroscopy (cordierite only), and transmission electron microscopy (TEM; cordierite only) analysis. In both cases, the impact of He- 4 cores (alpha particles) that were emitted from actinide-bearing mineral inclusions has caused the formation of radiation damage haloes in the host mineral. These haloes have maximum radii of about 33 mu m (chamosite) and 47 mu m (cordierite). They show notably changed optical properties, i.e., intensified absorption of light as recognised by brown (chamosite) and yellow (cordierite) pleochroism and enhanced or even anomalous interference colours. In spite of the significant disturbance of their short range order, alpha particle haloes are characterised by generally low degrees of structural radiation damage. This is indicated by rather moderate broadening of vibrational bands and, in the case of cordierite, apparently undisturbed electron diffraction patterns in the TEM. Intensive damage, virtually close to an amorphous state, was only found in cordierite up to a few tens of nanometres away from actinide-bearing inclusions. This damage is mainly assigned to recoils of heavy nuclei upon emission of an alpha particle, which have particle trajectory lengths that are three orders of magnitude shorter than those of the alpha particles. Similar to observations on biotite, alpha particle haloes in chamosite and cordierite as observed in the optical microscope may be considered as representative of a very early stage of the metamictisation process}, language = {en} } @misc{WirthKirschWlosczyketal.2016, author = {Wirth, Jonas and Kirsch, Harald and Wlosczyk, Sebastian and Tong, Yujin and Saalfrank, Peter and Kramer Campen, Richard}, title = {Characterization of water dissociation on α-Al2O3(1102)}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-394497}, pages = {14822 -- 14832}, year = {2016}, abstract = {The interaction of water with α-alumina (i.e. α-Al2O3) surfaces is important in a variety of applications and a useful model for the interaction of water with environmentally abundant aluminosilicate phases. Despite its significance, studies of water interaction with α-Al2O3 surfaces other than the (0001) are extremely limited. Here we characterize the interaction of water (D2O) with a well defined α-Al2O3(1[1 with combining macron]02) surface in UHV both experimentally, using temperature programmed desorption and surface-specific vibrational spectroscopy, and theoretically, using periodic-slab density functional theory calculations. This combined approach makes it possible to demonstrate that water adsorption occurs only at a single well defined surface site (the so-called 1-4 configuration) and that at this site the barrier between the molecularly and dissociatively adsorbed forms is very low: 0.06 eV. A subset of OD stretch vibrations are parallel to this dissociation coordinate, and thus would be expected to be shifted to low frequencies relative to an uncoupled harmonic oscillator. To quantify this effect we solve the vibrational Schr{\"o}dinger equation along the dissociation coordinate and find fundamental frequencies red-shifted by more than 1500 cm-1. Within the context of this model, at moderate temperatures, we further find that some fraction of surface deuterons are likely delocalized: dissociatively and molecularly absorbed states are no longer distinguishable.}, language = {en} } @article{WirthKirschWlosczyketal.2016, author = {Wirth, Jonas and Kirsch, Harald and Wlosczyk, Sebastian and Tong, Yujin and Saalfrank, Peter and Campen, Richard Kramer}, title = {Characterization of water dissociation on alpha-Al2O3(1(1)over-bar02): theory and experiment}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {18}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c6cp01397j}, pages = {14822 -- 14832}, year = {2016}, abstract = {The interaction of water with a-alumina (i.e. alpha-Al2O3) surfaces is important in a variety of applications and a useful model for the interaction of water with environmentally abundant aluminosilicate phases. Despite its significance, studies of water interaction with alpha-Al2O3 surfaces other than the (0001) are extremely limited. Here we characterize the interaction of water (D2O) with a well defined alpha-Al2O3(1 (1) over bar 02) surface in UHV both experimentally, using temperature programmed desorption and surface-specific vibrational spectroscopy, and theoretically, using periodic-slab density functional theory calculations. This combined approach makes it possible to demonstrate that water adsorption occurs only at a single well defined surface site (the so-called 1-4 configuration) and that at this site the barrier between the molecularly and dissociatively adsorbed forms is very low: 0.06 eV. A subset of OD stretch vibrations are parallel to this dissociation coordinate, and thus would be expected to be shifted to low frequencies relative to an uncoupled harmonic oscillator. To quantify this effect we solve the vibrational Schrodinger equation along the dissociation coordinate and find fundamental frequencies red-shifted by more than 1500 cm(-1). Within the context of this model, at moderate temperatures, we further find that some fraction of surface deuterons are likely delocalized: dissociatively and molecularly absorbed states are no longer distinguishable.}, language = {en} } @article{TongWirthKirschetal.2015, author = {Tong, Yujin and Wirth, Jonas and Kirsch, Harald and Wolf, Martin and Saalfrank, Peter and Campen, Richard Kramer}, title = {Optically probing Al-O and O-H vibrations to characterize water adsorption and surface reconstruction on alpha-alumina: An experimental and theoretical study}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {142}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {5}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4906346}, pages = {12}, year = {2015}, abstract = {Oxide/water interfaces are ubiquitous in a wide variety of applications and the environment. Despite this ubiquity, and attendant decades of study, gaining molecular level insight into water/oxide interaction has proven challenging. In part, this challenge springs from a lack of tools to concurrently characterize changes in surface structure (i.e., water/oxide interaction from the perspective of the solid) and O-H population and local environment (i.e., water/oxide interaction from the water perspective). Here, we demonstrate the application of surface specific vibrational spectroscopy to the characterization of the interaction of the paradigmatic alpha-Al2O3(0001) surface and water. By probing both the interfacial Al-O (surface phonon) and O-H spectral response, we characterize this interaction from both perspectives. Through electronic structure calculation, we assign the interfacial Al-O response and rationalize its changes on surface dehydroxylation and reconstruction. Because our technique is all-optical and interface specific, it is equally applicable to oxide surfaces in vacuum, ambient atmospheres and at the solid/liquid interface. Application of this approach to additional alumina surfaces and other oxides thus seems likely to significantly expand our understanding of how water meets oxide surfaces and thus the wide variety of phenomena this interaction controls. (C) 2015 AIP Publishing LLC.}, language = {en} } @article{KirschWirthTongetal.2014, author = {Kirsch, Harald and Wirth, Jonas and Tong, Yujin and Wolf, Martin and Saalfrank, Peter and Campen, Richard Kramer}, title = {Experimental characterization of unimolecular water dissociative adsorption on alpha-alumina}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {118}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {25}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/jp502106t}, pages = {13623 -- 13630}, year = {2014}, abstract = {alpha-Al2O3 surfaces are common in both engineered applications and the environment. Much prior work indicates that their properties, e.g., reactivity, polarity, and charge, change dramatically on interaction with water. Perhaps the simplest question that can be asked of alpha-Al2O3/water interaction is how a single water molecule interacts with the most stable alpha-Al2O3 surface: the alpha-Al2O3(0001). Over the last 15 years, a series of theoretical studies have found that water dissociatively adsorbs on alpha-Al2O3(0001) through two channels. However, to our knowledge no experimental evidence of these dissociation pathways has appeared. By combining sample preparation via supersonic molecular beam dosing, sample characterization via coherent, surface specific vibrational spectroscopy and electronic structure theory, we report the first experimental observation of reaction products of each, theoretically predicted, dissociation channel. These results thus overcome a 15 year old experiment/theory disconnect and make possible a variety of intriguing experiments that promise to provide significant new insights into water/Al2O3 and water/oxide interaction more generally.}, language = {en} } @article{HeidenWirthCampenetal.2018, author = {Heiden, Sophia and Wirth, Jonas and Campen, Richard Kramer and Saalfrank, Peter}, title = {Water molecular beam scattering at alpha-Al2O3(0001)}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {122}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {27}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.8b04179}, pages = {15494 -- 15504}, year = {2018}, abstract = {Recent molecular beam experiments have shown that water may adsorb molecularly or dissociatively on an α-Al2O3(0001) surface, with enhanced dissociation probability compared to "pinhole dosing", i.e., adsorption under thermal equilibrium conditions. However, precise information on the ongoing reactions and their relative probabilities is missing. In order to shed light on molecular beam scattering for this system, we perform ab initio molecular dynamics calculations to simulate water colliding with α-Al2O3(0001). We find that single water molecules hitting a cold, clean surface from the gas phase are either reflected, molecularly adsorbed, or dissociated (so-called 1-2 dissociation only). A certain minimum translational energy (above 0.1 eV) seems to be required to enforce dissociation, which may explain the higher dissociation probability in molecular beam experiments. When the surface is heated and/or when refined surface and beam models are applied (preadsorption with water or water fragments, clustering and internal preexcitation in the beam), additional channels open, among them physisorption, water clustering on the surface, and so-called 1-4 and 1-4′ dissociation.}, language = {en} } @article{HeidenYueKirschetal.2018, author = {Heiden, Sophia and Yue, Yanhua and Kirsch, Harald and Wirth, Jonas A. and Saalfrank, Peter and Campen, Richard Kramer}, title = {Water dissociative adsorption on α-Al2O3(112̅0) is controlled by surface site undercoordination, density, and topology}, series = {The journal of physical chemistry / publ. weekly by the American Chemical Society : C, Nanomaterials and interfaces}, volume = {122}, journal = {The journal of physical chemistry / publ. weekly by the American Chemical Society : C, Nanomaterials and interfaces}, number = {12}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.7b10410}, pages = {6573 -- 6584}, year = {2018}, abstract = {α-Al2O3 surfaces are common in a wide variety of applications and useful models of more complicated, environmentally abundant, alumino-silicate surfaces. While decades of work have clarified that all properties of these surfaces depend sensitively on the crystal face and the presence of even small amounts of water, quantitative insight into this dependence has proven challenging. Overcoming this challenge requires systematic study of the mechanism by which water interacts with various α-Al2O3 surfaces. Such insight is most easily gained for the interaction of small amounts of water with surfaces in ultra high vacuum. In this study, we continue our combined theoretical and experimental approach to this problem, previously applied to water interaction with the α-Al2O3 (0001) and (11̅02) surfaces, now to water interaction with the third most stable surface, that is, the (112̅0). Because we characterize all three surfaces using similar tools, it is straightforward to conclude that the (112̅0) is most reactive with water. The most important factor explaining its increased reactivity is that the high density of undercoordinated surface Al atoms on the (112̅0) surface allows the bidentate adsorption of OH fragments originating from dissociatively adsorbed water, while only monodentate adsorption is possible on the (0001) and (11̅02) surfaces: the reactivity of α-Al2O3 surfaces with water depends strongly, and nonlinearly, on the density of undercoordinated surface Al atoms.}, language = {en} } @article{SchultzeWirthWunderetal.2021, author = {Schultze, Dina and Wirth, Richard and Wunder, Bernd and Loges, Anselm and Wilke, Max and Franz, Gerhard}, title = {Corundum-quartz metastability}, series = {Contributions to mineralogy and petrology}, volume = {176}, journal = {Contributions to mineralogy and petrology}, number = {4}, publisher = {Springer}, address = {Berlin ; Heidelberg}, issn = {0010-7999}, doi = {10.1007/s00410-021-01786-5}, pages = {13}, year = {2021}, abstract = {The metastable paragenesis of corundum and quartz is rare in nature but common in laboratory experiments where according to thermodynamic predictions aluminum-silicate polymorphs should form. We demonstrate here that the existence of a hydrous, silicon-bearing, nanometer-thick layer (called "HSNL") on the corundum surface can explain this metastability in experimental studies without invoking unspecific kinetic inhibition. We investigated experimentally formed corundum reaction products synthesized during hydrothermal and piston-cylinder experiments at 500-800 degrees C and 0.25-1.8 GPa and found that this HSNL formed inside and on the corundum crystals, thereby controlling the growth behavior of its host. The HSNL represents a substitution of Al with Si and H along the basal plane of corundum. Along the interface of corundum and quartz, the HSNL effectively isolates the bulk phases corundum and quartz from each other, thus apparently preventing their reaction to the stable aluminum silicate. High temperatures and prolonged experimental duration lead to recrystallization of corundum including the HSNL and to the formation of quartz + fluid inclusions inside the host crystal. This process reduces the phase boundary area between the bulk phases, thereby providing further opportunity to expand their coexistence. In addition to its small size, its transient nature makes it difficult to detect the HSNL in experiments and even more so in natural samples. Our findings emphasize the potential impact of nanometer-sized phases on geochemical reaction pathways and kinetics under metamorphic conditions in one of the most important chemical systems of the Earth's crust.}, language = {en} }