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The reaction dynamics of methanol and water on Si(001) were investigated by means of molecular beam techniques. The initial sticking probability s0 was determined as a function of the kinetic energy of the incoming molecules, Ekin, and surface temperature, Ts. For both, methanol and water, a nonactivated reactional channel was observed; the dynamics were found to be determined by the reaction into the datively bonded intermediate state. A low conversion barrier was deduced for the conversion from this intermediate into the final state. It is attributed to the reaction mechanism, which proceeds via proton transfer from the OH-group of the datively bonded molecules to a Si surface atom. Despite this low conversion barrier, adsorption into the intermediate and further reaction via proton transfer were found to be largely decoupled. [ABSTRACT FROM AUTHOR]

Excitons are realizations of a correlated many-particle wave function, specifically consisting of electrons and holes in an entangled state. Excitons occur widely in semiconductors and are dominant excitations in semiconducting organic and low-dimensional quantum materials. To efficiently harness the strong optical response and high tuneability of excitons in optoelectronics and in energy-transformation processes, access to the full wavefunction of the entangled state is critical, but has so far not been feasible. Here, we show how time-resolved photoemission momentum microscopy can be used to gain access to the entangled wavefunction and to unravel the exciton's multiorbital electron and hole contributions. For the prototypical organic semiconductor buckminsterfullerene (C 60 ), we exemplify the capabilities of exciton tomography and achieve unprecedented access to key properties of the entangled exciton state including localization, charge-transfer character, and ultrafast exciton formation and relaxation dynamics., (© 2024. The Author(s).)

In two-dimensional semiconductors, cooperative and correlated interactions determine the material's excitonic properties and can even lead to the creation of correlated states of matter. Here, we study the fundamental two-particle correlated exciton state formed by the Coulomb interaction between single-particle holes and electrons. We find that the ultrafast transfer of an exciton's hole across a type II band-aligned semiconductor heterostructure leads to an unexpected sub-200-femtosecond upshift of the single-particle energy of the electron being photoemitted from the two-particle exciton state. While energy relaxation usually leads to an energetic downshift of the spectroscopic signature, we show that this upshift is a clear fingerprint of the correlated interaction of the electron and hole parts of the exciton. In this way, time-resolved photoelectron spectroscopy is straightforwardly established as a powerful method to access electron-hole correlations and cooperative behavior in quantum materials. Our work highlights this capability and motivates the future study of optically inaccessible correlated excitonic and electronic states of matter.

Mitochondrial dysfunction is a hallmark of cellular senescence and many age-related neurodegenerative diseases. We therefore investigated the relationship between mitochondrial function in peripheral blood cells and cerebral energy metabolites in young and older sex-matched, physically and mentally healthy volunteers. Cross-sectional observational study involving 65 young (26.0 ± 0.49 years) and 65 older (71.7 ± 0.71 years) women and men recruited. Cognitive health was evaluated using established psychometric methods (MMSE, CERAD). Blood samples were collected and analyzed, and fresh peripheral blood mononuclear cells (PBMCs) were isolated. Mitochondrial respiratory complex activity was measured using a Clarke electrode. Adenosine triphosphate (ATP) and citrate synthase activity (CS) were determined by bioluminescence and photometrically. N-aspartyl-aspartate (tNAA), ATP, creatine (Cr), and phosphocreatine (PCr) were quantified in brains using 1 H- and 31 P-magnetic resonance spectroscopic imaging (MRSI). Levels of insulin-like growth factor 1 (IGF-1) were determined using a radio-immune assay (RIA). Complex IV activity (CIV) (- 15%) and ATP levels (- 11%) were reduced in PBMCs isolated from older participants. Serum levels of IGF-1 were significantly reduced (- 34%) in older participants. Genes involved in mitochondrial activity, antioxidant mechanisms, and autophagy were unaffected by age. tNAA levels were reduced (- 5%), Cr (+ 11%), and PCr (+ 14%) levels were increased, and ATP levels were unchanged in the brains of older participants. Markers of energy metabolism in blood cells did not significantly correlate with energy metabolites in the brain. Age-related bioenergetic changes were detected in peripheral blood cells and the brains of healthy older people. However, mitochondrial function in peripheral blood cells does not reflect energy related metabolites in the brain. While ATP levels in PBMCs may be be a valid marker for age-related mitochondrial dysfunction in humans, cerebral ATP remained constant., (© 2023. The Author(s).)

Twisted bilayer graphene provides an ideal solid-state model to explore correlated material properties and opportunities for a variety of optoelectronic applications, but reliable, fast characterization of the twist angle remains a challenge. Here we introduce spectroscopic ellipsometric contrast microscopy (SECM) as a tool for mapping twist angle disorder in optically resonant twisted bilayer graphene. We optimize the ellipsometric angles to enhance the image contrast based on measured and calculated reflection coefficients of incident light. The optical resonances associated with van Hove singularities correlate well to Raman and angle-resolved photoelectron emission spectroscopy, confirming the accuracy of SECM. The results highlight the advantages of SECM, which proves to be a fast, nondestructive method for characterization of twisted bilayer graphene over large areas, unlocking process, material, and device screening and cross-correlative measurement potential for bilayer and multilayer materials.

Objectives: Human nutrition plays an important role in prevention or at least slowing down the progression of age- and diet-related diseases. Thereby, mitochondrial dysfunction represents one common underlying mechanism, which is being investigated in mouse models. However, the influence of the selected diets in preclinical studies on cognition and mitochondrial function has not yet been reported cohesively. Methods: Therefore, we present the results of three different studies that addressed this question. First, we investigated the influence of two standard control chow diets and a special diet low in antioxidants over 6 months in aged NMRI mice. Additionally, a 70% high-fat (HF) chow diet as well as a western-style diet (WSD) rich in lard and fructose were examined in C57/BL6 mice. Cognitive performance, mitochondrial function and bioenergetics in the brain were investigated. Moreover, cerebral expression of genes involved in biogenesis and antioxidant defence (citrate synthase, complex I, complex IV, SOD2, Cat1, GPx-1) were quantified. Results: The results show that a modified, low antioxidant diet increased ATP levels in the brain of aged mice, while cognitive functions remained largely unaffected. A HF diet also showed significant effects on ATP levels and gene expression levels of relevant antioxidant markers, while the WSD had marginal effects on mitochondrial function and bioenergetics in the brain. Discussion: Our results indicate that standard- and special diets have an impact on cognition and mitochondrial function in the brain. Thus, appropriate caution is warranted when selecting a suitable diet for preclinical studies in mice.

Moiré superlattices in atomically thin van der Waals heterostructures hold great promise for extended control of electronic and valleytronic lifetimes 1-7 , the confinement of excitons in artificial moiré lattices 8-13 and the formation of exotic quantum phases 14-18 . Such moiré-induced emergent phenomena are particularly strong for interlayer excitons, where the hole and the electron are localized in different layers of the heterostructure 19,20 . To exploit the full potential of correlated moiré and exciton physics, a thorough understanding of the ultrafast interlayer exciton formation process and the real-space wavefunction confinement is indispensable. Here we show that femtosecond photoemission momentum microscopy provides quantitative access to these key properties of the moiré interlayer excitons. First, we elucidate that interlayer excitons are dominantly formed through femtosecond exciton-phonon scattering and subsequent charge transfer at the interlayer-hybridized Σ valleys. Second, we show that interlayer excitons exhibit a momentum fingerprint that is a direct hallmark of the superlattice moiré modification. Third, we reconstruct the wavefunction distribution of the electronic part of the exciton and compare the size with the real-space moiré superlattice. Our work provides direct access to interlayer exciton formation dynamics in space and time and reveals opportunities to study correlated moiré and exciton physics for the future realization of exotic quantum phases of matter., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Comprehending far-from-equilibrium many-body interactions is one of the major goals of current ultrafast condensed matter physics research. Here, a particularly interesting but barely understood situation occurs during a strong optical excitation, where the electron and phonon systems can be significantly perturbed and the quasiparticle distributions cannot be described with equilibrium functions. In this work, we use time- and angle-resolved photoelectron spectroscopy to study such far-from-equilibrium many-body interactions for the prototypical material graphene. In accordance with theoretical simulations, we find remarkable transient renormalizations of the quasiparticle self-energy caused by the photoinduced nonequilibrium conditions. These observations can be understood by ultrafast scatterings between nonequilibrium electrons and strongly coupled optical phonons, which signify the crucial role of ultrafast nonequilibrium dynamics on many-body interactions. Our results advance the understanding of many-body physics in extreme conditions, which is important for any endeavor to optically manipulate or create non-equilibrium states of matter.

Aging is the main risk factor for sporadic Alzheimer's disease (AD), which is characterized by the cerebral deposition of β-amyloid peptides (Aβ) and cognitive decline. Mitochondrial dysfunction is also characteristic of the disease and represents a hallmark of both, aging and neurodegeneration. We longitudinally followed Aβ levels, cognition, and mitochondrial function in the same cohort of Thy1-APP 751 SL mice representing a murine model of AD. In the course of time, changes were most prominent at an age of 13 months including the latency time in the passive avoidance test, the activity of complexes I and IV of the mitochondrial respiration chain, and expression of genes related to mitochondrial biogenesis and synaptic plasticity including Peroxisome proliferator-activated receptor gamma coactivator 1-alpha (PGC1-α), CAMP responsive element binding protein 1 (CREB1), and Synaptophysin 1 (SYP1). These changes occurred in parallel with massively increasing cerebral Aβ levels. Other parameters were changed in younger mice including the alteration rate in the Y-maze test and the nesting score when Aβ levels were not changed yet. The results are consistent in the cohort described. However, previous, non-longitudinal studies reported divergent time points for the occurrence of the parameters studied. These findings are discussed in light of the current results., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Reutzel, Grewal, Joppe and Eckert.)

Scope: To further examine the role of the human milk oligosaccharide 2'fucosyllactose (2´FL) and fucose (Fuc) in cognition. Using 13 C-labeled 2'FL,thestudy previously showed in mice that 13 C-enrichment of the brain is not caused by 13 C 1 -2´FL itself, but rather by microbial metabolites. Here, the study applies 13 C 1 -Fuc in the same mouse model to investigate its uptake into the brain., Methods and Results: Mice received 13 C 1 -Fuc via oral gavage (2 mmol 13 C 1 -Fuc/kg -1 body weight) or intravenously (0.4 mmol/kg -1 body weight). 13 C-enrichment is measured in organs, including various brain regions, biological fluids and excrements. By EA-IRMS, the study observes an early rise of 13 C-enrichment in plasma, 30 min after oral dosing. However, 13 C-enrichment in the brain does not occur until 3-5 h post-dosing, when the 13 C-Fuc bolus has already reached the lower gut. Therefore, the researcher assume that 13 C-Fuc is absorbed in the upper small intestine but cannot cross the blood-brain barrier which is also observed after intravenous application of 13 C 1 -Fuc., Conclusions: Late 13 C-enrichment in the rodent brain may be derived from 13 C 1 -Fuc metabolites derived from bacterial fermentation. The precise role that Fuc or 2´FL metabolites might play in gut-brain communication needs to be investigated in further studies., (© 2021 The Authors. Molecular Nutrition & Food Research published by Wiley-VCH GmbH.)

As components of the Mediterranean diet (MedDiet) olive polyphenols may play a crucial role for the prevention of Alzheimer's disease (AD). Since mitochondrial dysfunction is involved in both, brain ageing and early AD, effects of 10 different purified phenolic secoiridoids (hydroxytyrosol, tyrosol, oleacein, oleuroside, oleuroside aglycon, oleuropein, oleocanthal, ligstroside, ligstroside aglycone and ligustaloside B) and two metabolites (the plant metabolite elenolic acid and the mammalian metabolite homovanillic acid) were tested in very low doses on mitochondrial function in SH-SY5Y-APP 695 cells - a cellular model of early AD. All tested secoiridoids significantly increased basal adenosine triphosphate (ATP) levels in SY5Y-APP 695 cells. Oleacein, oleuroside, oleocanthal and ligstroside showed the highest effect on ATP levels and were additionally tested on mitochondrial respiration. Only oleocanthal and ligstroside were able to enhance the capacity of respiratory chain complexes. To investigate their underlying molecular mechanisms, the expression of genes associated with mitochondrial biogenesis, respiration and antioxidative capacity (PGC-1α, SIRT1, CREB1, NRF1, TFAM, complex I, IV and V, GPx1, SOD2, CAT) were determined using qRT-PCR. Exclusively ligstroside increased mRNA expression of SIRT1, CREB1, complex I, and GPx1. Furthermore, oleocanthal but not ligstroside decreased Aβ 1-40 levels in SH-SY5Y-APP 695 cells. To investigate the in vivo effects of purified secoiridoids, the two most promising compounds (oleocanthal and ligstroside) were tested in a mouse model of ageing. Female NMRI mice, aged 12 months, received a diet supplemented with 50 mg/kg oleocanthal or ligstroside for 6 months (equivalent to 6.25 mg/kg b.w.). Young (3 months) and aged (18 months) mice served as controls. Ligstroside fed mice showed improved spatial working memory. Furthermore, ligstroside restored brain ATP levels in aged mice and led to a significant life extension compared to aged control animals. Our findings indicate that purified ligstroside has outstanding performance on mitochondrial bioenergetics in models of early AD and brain ageing by mechanisms that may not interfere with Aβ production. Additionally, ligstroside expanded the lifespan in aged mice and enhanced cognitive function., Competing Interests: Declaration of Competing Interest The authors declare that they have no conflict of interest., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Depending on the applied strength, electromagnetic fields in electronic materials can induce dipole transitions between eigenstates or distort the Coulomb potentials that define them. Between the two regimes, they can also modify the electronic properties in more subtle ways when electron motion becomes governed by time and space-periodic potentials. The optical field introduces new virtual bands through Floquet engineering that under resonant conditions interacts strongly with the preexisting bands. Under such conditions the virtual bands can become real, and real ones become virtual as the optical fields and electronic band dispersions entangle the electronic response. We reveal optical dressing of electronic bands in a metal by exciting four-photon photoemission from the Cu(111) surface involving a three-photon resonant transition from the Shockley surface band to the first image potential band. Attosecond resolved interferometric scanning between identical pump-probe pulses and its Fourier analysis reveal how the optical field modifies the electronic properties of a solid through combined action of dipole excitation and field dressing.

Brain aging is one of the major risk factors for the development of several neurodegenerative diseases. Therefore, mitochondrial dysfunction plays an important role in processes of both, brain aging and neurodegeneration. Aged mice including NMRI mice are established model organisms to study physiological and molecular mechanisms of brain aging. However, longitudinal data evaluated in one cohort are rare but are important to understand the aging process of the brain throughout life, especially since pathological changes early in life might pave the way to neurodegeneration in advanced age. To assess the longitudinal course of brain aging, we used a cohort of female NMRI mice and measured brain mitochondrial function, cognitive performance, and molecular markers every 6 months until mice reached the age of 24 months. Furthermore, we measured citrate synthase activity and respiration of isolated brain mitochondria. Mice at the age of three months served as young controls. At six months of age, mitochondria-related genes (complex IV, creb-1, β -AMPK, and Tfam) were significantly elevated. Brain ATP levels were significantly reduced at an age of 18 months while mitochondria respiration was already reduced in middle-aged mice which is in accordance with the monitored impairments in cognitive tests. mRNA expression of genes involved in mitochondrial biogenesis (cAMP response element-binding protein 1 (creb-1), peroxisome proliferator-activated receptor gamma coactivator 1-alpha (PGC1- α ), nuclear respiratory factor-1 (Nrf-1), mitochondrial transcription factor A (Tfam), growth-associated protein 43 (GAP43), and synaptophysin 1 (SYP1)) and the antioxidative defense system (catalase (Cat) and superoxide dismutase 2 (SOD2)) was measured and showed significantly decreased expression patterns in the brain starting at an age of 18 months. BDNF expression reached, a maximum after 6 months. On the basis of longitudinal data, our results demonstrate a close connection between the age-related decline of cognitive performance, energy metabolism, and mitochondrial biogenesis during the physiological brain aging process., Competing Interests: The authors declare that they have no conflicts of interest., (Copyright © 2020 Martina Reutzel et al.)

Photons can excite collective and single-particle excitations in metals; the collective plasmonic excitations are of keen interest in physics, chemistry, optics, and nanotechnology because they enhance coupling of electromagnetic energy and can drive nonlinear processes in electronic materials, particularly where their dielectric function ϵ(ω) approaches zero. We investigate the nonlinear angle-resolved two-photon photoemission (2PP) spectroscopy of the Ag(111) surface through the ϵ(ω) near-zero region. In addition to the Einsteinian single-particle photoemission, the 2PP spectra report unequivocal signatures of nonlocal dielectric, plasmonically enhanced, excitation processes.

Scope: 2´-Fucosyllactose (2´FL) is an abundant oligosaccharide in human milk. It is hypothesized that its brain enrichment is associated with improved learning. Accumulation of 2´FL in organs, biological fluids, and feces is assessed in wild-type and germ-free mice., Methods and Results: 13 C-labelled 2´FL is applied to NMRI wild-type mice intravenously (0.2 g kg -1 ) or orally (1 g kg -1 ), while controls receive saline. Biological samples are collected (0.5-15 h) and 13 C-enrichment is measured by elemental analysis isotope ratio mass spectrometry (EA-IRMS). After oral application, 2´FL is primarily eliminated in the feces. 13 C-enrichment in organs including the brain follows the same pattern as in plasma with a maximum peak after 5 h. However, 13 C-enrichment is only detected when the 13 C-2´FL bolus reaches the colon. In contrast, in germ-free mice, the 13 C-bolus remains in the intestinal content and is expelled via the feces. Furthermore, intravenously applied 13 C-2´FL is eliminated via urine; no 13 C-enrichment of organs is observed, suggesting that intact 2´FL is not retained., Conclusions: 13 C-enrichment in brain and other organs after oral application of 13 C-2´FL in wild-type mice indicates cleaved fucose or other gut microbial 2´FL metabolites may be incorporated, as opposed to intact 2´FL., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Controlling chemical reactions beyond thermally activated reaction schemes can open alternative reaction channels, and thus lead to new final products. Herein, we show for tetrahydrofuran (THF) cleavage on Si(001), the surface analogue of an S N 2 reaction, that excitation by electrons from the tip of a scanning tunneling microscope (STM) not only opens new reaction channels, but that different final products can be selectively addressed by the type of excitation: Above a threshold voltage of 2.5 V, direct excitation by electron transfer into the antibonding C-O orbital of the THF molecules induces ether cleavage of the datively bonded intermediate of THF on Si(001). Below the threshold, ether cleavage is induced by multiple excitation of vibrational modes. In both modes of excitation, additional final configurations were observed when compared to the thermally activated reaction. The branching ratios of the final configurations are different for the two different excitation mechanisms, which in turn can be controlled by the applied sample bias., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Aging represents a major risk factor for developing neurodegenerative diseases such as Alzheimer's disease (AD). As components of the Mediterranean diet, olive polyphenols may play a crucial role in the prevention of AD. Since mitochondrial dysfunction acts as a final pathway in both brain aging and AD, respectively, the effects of a mixture of highly purified olive secoiridoids were tested on cognition and ATP levels in a commonly used mouse model for brain aging. Over 6 months, female NMRI mice (12 months of age) were fed with a blend containing highly purified olive secoiridoids (POS) including oleuropein, hydroxytyrosol and oleurosid standardized for 50 mg oleuropein/kg diet (equivalent to 13.75 mg POS/kg b.w.) or the study diet without POS as control. Mice aged 3 months served as young controls. Behavioral tests showed deficits in cognition in aged mice. Levels of ATP and mRNA levels of NADH-reductase, cytochrome-c-oxidase, and citrate synthase were significantly reduced in the brains of aged mice indicating mitochondrial dysfunction. Moreover, gene expression of Sirt1, CREB, Gap43, and GPx-1 was significantly reduced in the brain tissue of aged mice. POS-fed mice showed improved spatial working memory. Furthermore, POS restored brain ATP levels in aged mice which were significantly increased. Our results show that a diet rich in purified olive polyphenols has positive long-term effects on cognition and energy metabolism in the brain of aged mice.

Background: Current approved drugs for Alzheimer's disease (AD) only attenuate symptoms, but do not cure the disease. The pirinixic acid derivate MH84 has been characterized as a dual gamma-secretase/proliferator activated receptor gamma (PPARγ) modulator in vitro. Pharmacokinetic studies in mice showed that MH84 is bioavailable after oral administration and reaches the brain. We recently demonstrated that MH84 improved mitochondrial dysfunction in a cellular model of AD. In the present study, we extended the pharmacological characterization of MH84 to 3-month-old Thy-1 AβPP SL mice (harboring the Swedish and London mutation in human amyloid precursor protein (APP)) which are characterized by enhanced AβPP processing and cerebral mitochondrial dysfunction, representing a mouse model of early AD., Methods: Three-month-old Thy-1 AβPP SL mice received 12 mg/kg b.w. MH84 by oral gavage once a day for 21 days. Mitochondrial respiration was analyzed in isolated brain mitochondria, and mitochondrial membrane potential and ATP levels were determined in dissociated brain cells. Citrate synthase (CS) activity was determined in brain tissues and MitoTracker Green fluorescence was measured in HEK293-AβPPwt and HEK293-AβPPsw cells. Soluble Aβ 1-40 and Aβ 1-42 levels were determined using ELISA. Western blot analysis and qRT-PCR were used to measure protein and mRNA levels, respectively., Results: MH84 reduced cerebral levels of the β-secretase-related C99 peptide and of Aβ40 levels. Mitochondrial dysfunction was ameliorated by restoring complex IV (cytochrome-c oxidase) respiration, mitochondrial membrane potential, and levels of ATP. Induction of PPARγ coactivator-1α (PGC-1α) mRNA and protein expression was identified as a possible mode of action that leads to increased mitochondrial mass as indicated by enhanced CS activity, OXPHOS levels, and MitoTracker Green fluorescence., Conclusions: MH84 modulates β-secretase processing of APP and improves mitochondrial dysfunction by a PGC-1α-dependent mechanism. Thus, MH84 seems to be a new promising therapeutic agent with approved in-vivo activity for the treatment of AD.

Several studies suggest that intake of omega-3 polyunsaturated fatty acids (n3-PUFA) beneficially influences cognitive function. However, effects on the adult brain are not clear. Little is known about the impact of dietary intervention on the fatty acid profile in adult brain, the modulation in the expression of enzymes involved in fatty acid biosynthesis and metabolism as well as changes in resulting oxylipins. These questions were addressed in the present study in two independent n3-PUFA feeding experiments in mice. Supplementation of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA, 1% each in the diet) for 30days to adult NMRI and C57BL/6 mice led to a distinct shift in the brain PUFA pattern. While n3-PUFAs EPA, n3 docosapentaenoic acid and DHA were elevated, many n6-PUFAs were significantly decreased (except, e.g. C20:3 n6 which was increased). This shift in PUFAs was accompanied by immense differences in concentrations of oxidative metabolites derived from enzymatic conversion of PUFAs, esp. arachidonic acid whose products were uniformly decreased, and a modulation in the activity and expression pattern of delta-5 and delta-6 desaturases. In both mouse strains a remarkable increase in the soluble epoxide hydrolase (sEH) activity (decreased epoxy-FA concentrations and epoxy-FA to dihydroxy-FA-ratios) as well as sEH expression was observed. Taking the high biological activity of epoxy-FA, e.g. on blood flow and nociceptive signaling into account, this finding might be of relevance for the effects of n3-PUFAs in neurodegenerative diseases. On any account, our study suggests a new distinct regulation of brain PUFA and oxylipin pattern by supplementation of n3-PUFAs to adult rodents., (Copyright © 2017 Elsevier Inc. All rights reserved.)

We combine density functional theory calculations and scanning tunneling microscopy investigations to identify the relevant chemical species and reactions in the nucleation phase of chemical vapor deposition. tert-Butylphosphine (TBP) was deposited on a silicon substrate under conditions typical for surface functionalization and growth of semiconductor materials. On the activated hydrogen-covered surface H/Si(001) it forms a strong covalent P-Si bond without loss of the tert-butyl group. Calculations show that site preference for multiple adsorption of TBP is influenced by steric repulsion of the adsorbate's bulky substituent. STM imaging furthermore revealed an anisotropic distribution of TBP with a preference for adsorption perpendicular to the surface dimer rows. The adsorption patterns found can be understood by a mechanism invoking stabilization of surface hydrogen vacancies through electron donation by an adsorbate. The now improved understanding of nucleation in thin-film growth may help to optimize molecular precursors and experimental conditions and will ultimately lead to higher quality materials., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The key parameters of the potential energy curve of organic molecules on semiconductor surfaces, binding energy of the intermediate state and dissociation barrier, were experimentally investigated for the model system of diethyl ether (Et2O) on Si(001). Et2O adsorbs via a datively bonded intermediate from which it converts via ether cleavage into a covalently attached final state. This thermally activated conversion into the final state was followed in real-time by means of optical second-harmonic generation (SHG) at different temperatures and the associated energy barrier ϵa = 0.38 ± 0.05 eV and pre-exponential factor νa = 10(4±1) s(-1) were determined. From molecular beam experiments on the initial sticking probability, the difference between the desorption energy ϵd and ϵa was extracted and thus the binding energy of the intermediate state was determined (0.62 ± 0.08 eV). The results are discussed in terms of general chemical trends as well as with respect to a wider applicability on adsorbate reactions on semiconductor surfaces.