共查询到20条相似文献,搜索用时 375 毫秒
1.
Areeg Abdelrahman Johannes M. Hermann Prof. Dr. Timo Jacob Dr. Ludwig A. Kibler 《Chemphyschem》2019,20(22):2989-2996
The adsorption of acetate on an Au(111) electrode surface in contact with acetic acid at pH 2.7 was imaged in-situ using scanning tunnelling microscopy (STM). Two different ordered structures were imaged for acetate adsorbed in the bidentate configuration on the unreconstructed surface at 0.95 V (vs. the saturated calomel electrode, SCE). The first structure, , is metastable and transforms at constant potential within 20 minutes to a structure, which is thermodynamically more favourable. The acetate adlayer starts to form at step edges and propagates via nucleation and growth onto terraces. The findings from in-situ STM are in agreement with the electrochemical behaviour of acetate on Au(111) characterized by voltammetry. A comparison is made with formate adsorption on Au(111). While acetate is not reactive, in contrast to formate, it can act as a spectator species in formic acid electrooxidation. 相似文献
2.
Dr. Dominique Marion Dr. Diego F. Gauto Isabel Ayala Karine Giandoreggio-Barranco Dr. Paul Schanda 《Chemphyschem》2019,20(2):276-284
Studying protein dynamics on microsecond-to-millisecond (μs-ms) time scales can provide important insight into protein function. In magic-angle-spinning (MAS) NMR, μs dynamics can be visualized by rotating-frame relaxation dispersion experiments in different regimes of radio-frequency field strengths: at low RF field strength, isotropic-chemical-shift fluctuation leads to “Bloch-McConnell-type” relaxation dispersion, while when the RF field approaches rotary resonance conditions bond angle fluctuations manifest as increased rate constants (“Near-Rotary-Resonance Relaxation Dispersion”, NERRD). Here we explore the joint analysis of both regimes to gain comprehensive insight into motion in terms of geometric amplitudes, chemical-shift changes, populations and exchange kinetics. We use a numerical simulation procedure to illustrate these effects and the potential of extracting exchange parameters, and apply the methodology to the study of a previously described conformational exchange process in microcrystalline ubiquitin. 相似文献
3.
Dr. Michele Porto Prof. Ruggero Angelico Dr. Pietro Calandra Dr. Valeria Loise Dr. Abraham A. Abe Prof. Cesare Oliviero Rossi Dr. Paolino Caputo 《Chemphyschem》2023,24(24):e202300217
In this investigation the dynamics of two types of bitumens with different penetration grade were tested by using dynamic shear rheometry (DSR) and Nuclear Magnetic Resonance (NMR) at unaged conditions, and upon both short- and long-term artificial aging. The gel-sol transition temperature was found to increase with increasing the time of aging treatment. Arrhenius parameters of the viscosity were found, unexpectedly, to be correlated with those of simple liquids, suggesting that the two kinds of systems, although chemically and physically quite different, share the same basic process at the molecular level. The molecular dynamics has been then investigated by NMR Pulsed Field Gradient Stimulated-Echo (PFGSE) and relaxometry (Carr-Purcell-Meiboom-Gill, CPMG, spin-echo pulse sequence) to capture the effect of aging upon dynamics variables such as self-diffusion coefficients D and transverse relaxation times T2. The translational diffusion at T> of the light molecular components of both types of bitumens was characterized by broad distributions of D which were found independent of the experimental time scale up to 0.2 s. Similarly, T2 data could be described as a continuous unimodal distributions of relaxation times determined both at T< and T> . 相似文献
4.
Prof. Dr. Donald McNaughton Dr. Dennis Wachsmuth Dr. Peter Kraus Dr. Sven Herbers Dr. Juan Wang Prof. Dr. Jens-Uwe Grabow 《Chemphyschem》2021,22(16):1692-1697
An accurate semi-experimental equilibrium structure of 8-hydroxyquinoline (8-HQ) has been determined combining experiment and theory. The cm-wave rotational spectrum of 8-HQ was recorded in a pulsed supersonic jet using broadband dual-path reflection and narrowband Fabry-Perot-type resonator Fourier-transform microwave spectrometers. Accurate rotational and quartic centrifugal distortion constants and 14N quadrupole coupling constants are determined. Rotational constants of all 13C, 18O and 15N singly substituted isotopologues in natural abundance and those of a chemically synthesized OD isotopologue were used to obtain geometric parameters for all the heavy atoms and the hydroxyl hydrogen from a number of structure determination models. Theoretical approaches allowed for the determination of a semi-experimental equilibrium structure, in which computed rovibrational and electronic corrections were utilized to convert vibrational ground state constants into equilibrium constants. Despite the molecule having only a horizontal plane of symmetry and possessing 11 individual heavy atoms, microwave spectroscopy has allowed for a reliable and accurate structure determination. A mass dependent, structure was determined and proved to be equally reliable by comparison with the B3LYP-D3(BJ)/aVTZ equilibrium structure. 相似文献
5.
Patrick Hemberger Zeyou Pan Andras Bodi Jeroen A. van Bokhoven Thomas K. Ormond G. Barney Ellison Nadav Genossar Joshua H. Baraban 《Chemphyschem》2020,21(19):2217-2222
Unveiling reaction mechanisms by isomer-selective detection of reactive intermediates requires advanced spectroscopic knowledge. We study the photoionization of fulvenone (c-C5H4=C=O), a reactive ketene species relevant in catalytic pyrolysis of lignin, which was generated by pyrolysis of 2-methoxy acetophenone. The high-resolution threshold photoelectron spectrum (TPES) with vacuum ultraviolet synchrotron radiation revealed well-resolved vibrational transitions, assigned to ring deformation modes of the cyclopentadiene moiety. The adiabatic ionization energy was determined to be 8.25±0.01 eV and is assigned to the 2A2← 1A1 transition. A broad and featureless band arising at 9 eV is associated with the 2B1← 1A1 excitation. A conical intersection is responsible for the ultrafast relaxation of the fulvenone cation from the into the state resulting in a featureless and lifetime broadened band. These insights will increase the detection capabilities for fulvenone and thereby help to elucidate reaction mechanisms in lignin catalytic pyrolysis. 相似文献
6.
Prof. Dr. Sunghun Jung Dr. Joon Kyo Seo Dr. Il-Chan Jang Dr. Jihun Kim Prof. Dr. Jae-Hyun Shim Dr. Jung-Je Woo 《Chemphyschem》2023,24(21):e202300438
We defined four major deterioration factors (electrolyte loss (EL), lithium loss (LL), lithium precipitation (LP), and compound deterioration (CD)). Then, we derived eleven key performance indicators (KPIs) for comparative analysis. After that, we fabricated three deteriorated cells for each of three deterioration factors (EL, LL, and LP) and one cell with CD (for verification) with four individual (dis)charging experiment manuals. The two major contributions of this study are the performance of 1) trend analysis to determine a suitable diagnostic metric by inspecting the eleven KPIs and 2) comparison analysis of and to verify the effectiveness of utilizing as a real-time deterioration diagnostic factor using a concept of model-in-the-loop simulation. The results show that 1) has the most conspicuous trendline tendency among the eleven comparison targets for all four major deterioration factors, and 2) the angle difference between the two trends of and lies within a minimum of 9° and a maximum of 43° (with a sscale on the x-axis and a scale on the y-axis for a clear trend line analysis). From this, we can conclude that the trendline-based real-time deterioration analysis employing may be practically applicable to a limited extent. 相似文献
7.
Ignacio Benito-Gómez Prof. Luis Méndez Dr. Jaime Suárez Prof. Jimena D. Gorfinkiel Dr. Ismanuel Rabadán 《Chemphyschem》2023,24(19):e202300305
We have investigated the dissociation of a resonant state that can be formed in low energy electron scattering from H2O+. We have chosen the second triplet resonance above the state of H2O+ whose autoionization mainly produces H2O+ ( ). We have considered both dissociation of the resonant state itself, dissociative recombination (DR), or the dissociation of the H2O+ cation after autodetachment, dissociative excitation (DE). The time-evolution of a wave packet on the potential energy surfaces of the resonance and cationic states shows, for the initial conditions studied, that the probability for DR is about 38 % while the probability for DE is negligible. 相似文献
8.
Dr. Luís P. Viegas 《Chemphyschem》2023,24(16):e202300259
Experimental work on the OH-initiated oxidation reactions of fluorotelomer aldehydes (FTALs) strongly suggests that the respective rate coefficients do not depend on the size of the CxF2x+1 fluoroalkyl chain. FTALs hence represent a challenging test to our multiconformer transition state theory (MC-TST) protocol based on constrained transition state randomization (CTSR), since the calculated rate coefficients should not show significant variations with increasing values of . In this work we apply the MC-TST/CTSR protocol to the cases and calculate both rate coefficients at 298.15 K with a value of cm3 molecule−1 s−1, practically coincident with the recommended experimental value of kexp= cm3 molecule−1 s−1. We also show that the use of tunneling corrections based on improved semiclassical TST is critical in obtaining Arrhenius-Kooij curves with a correct behavior at lower temperatures. 相似文献
9.
We study the kinetics of hydrogen sorption in Mg-Ti-H nanoparticles prepared by gas phase condensation of mixed Mg-Ti vapors under a H2-containing atmosphere. Four samples with different Ti contents from 14 to 63 at.% Ti are examined in the 100–150 °C range. The hydrogen absorption kinetics coupled with the formation of MgH2 can be described by a nucleation and growth model. The activation energy is in the range kJ/mol and the rate constant (at 150 °C) increases from s−1 to s−1 with increasing Ti content. Hydrogen desorption is well modeled by a sequence of surface-limited and contracting-volume kinetics, except at the highest Ti content where nucleation and growth is observed. The activation energy of surface-limited kinetics is /mol. The rate constant (at 150 °C) increases from s−1 to s−1 with the Ti content. These results open an unexplored kinetic window for Mg-based reversible hydrogen storage close to ambient temperature. 相似文献
10.
Prof. Dr. S. Schippers Dr. P.-M. Hillenbrand Dr. A. Perry-Sassmannshausen Dr. T. Buhr S. Fuchs S. Reinwardt Dr. F. Trinter Prof. Dr. A. Müller Dr. M. Martins 《Chemphyschem》2023,24(11):e202300061
Carbon 1s core-hole excitation of the molecular anion C2− has been experimentally studied at high resolution by employing the photon-ion merged-beams technique at a synchrotron light source. The experimental cross section for photo–double-detachment shows a pronounced vibrational structure associated with and core excitations of the C2− ground level and first excited level, respectively. A detailed Franck-Condon analysis reveals a strong contraction of the C2− molecular anion by 0.2 Å upon this core photoexcitation. The associated change of the molecule's moment of inertia leads to a noticeable rotational broadening of the observed vibrational spectral features. This broadening is accounted for in the present analysis which provides the spectroscopic parameters of the C2− and core-excited levels. 相似文献
11.
Prof. Dr. Stanka Jerosimić Assist. Prof. Dr. Milan Milovanović Assist. Dr. Marko Mitić Univ.-Prof. Dr. Roland Wester Prof. Dr. Dr. h. c. Francesco A. Gianturco 《Chemphyschem》2023,24(22):e202300248
We present results of quantum structure calculations aimed at demonstrating the possible existence of dipole-bound states (DBS) for the anion , a species already detected in the Interstellar medium (ISM). The positive demonstration of DBS existence using ab initio studies is an important step toward elucidating possible pathways for the formation of the more tightly bound valence bound states (VBS) in environments where free electrons from starlight ionization processes are known to be available to interact with the radical partner of the title molecule. Our current calculations show that such excited DBS states can exist in , in agreement with what we had previously found for the smallercyanopolyyne in the series: the anion. This system has a very weakly bound anion with binding energies of about 3 and 9 cm−1 for the and DBS, respectively. 相似文献
12.
Atomic-Scale Studies of Fe3O4(001) and TiO2(110) Surfaces Following Immersion in CO2-Acidified Water
Dr. Francesca Mirabella Dr. Jan Balajka Dr. Jiri Pavelec Markus Göbel Florian Kraushofer Prof. Dr. Michael Schmid Prof. Dr. Gareth S. Parkinson Prof. Dr. Ulrike Diebold 《Chemphyschem》2020,21(16):1788-1796
Difficulties associated with the integration of liquids into a UHV environment make surface-science style studies of mineral dissolution particularly challenging. Recently, we developed a novel experimental setup for the UHV-compatible dosing of ultrapure liquid water and studied its interaction with TiO2 and Fe3O4 surfaces. Herein, we describe a simple approach to vary the pH through the partial pressure of CO2 ( ) in the surrounding vacuum chamber and use this to study how these surfaces react to an acidic solution. The TiO2(110) surface is unaffected by the acidic solution, except for a small amount of carbonaceous contamination. The Fe3O4(001)-( × )R45° surface begins to dissolve at a pH 4.0–3.9 ( =0.8–1 bar) and, although it is significantly roughened, the atomic-scale structure of the Fe3O4(001) surface layer remains visible in scanning tunneling microscopy (STM) images. X-ray photoelectron spectroscopy (XPS) reveals that the surface is chemically reduced and contains a significant accumulation of bicarbonate (HCO3−) species. These observations are consistent with Fe(II) being extracted by bicarbonate ions, leading to dissolved iron bicarbonate complexes (Fe(HCO3)2), which precipitate onto the surface when the water evaporates. 相似文献
13.
Rate constants for the reactions of muonium (Mu) (the ultralight isotope of the hydrogen atom) with H2O2 in H2O and D2O2 in D2O have been determined at various temperatures and pH (pD) values. The data are consistent with the three reactions: , , and the equivalent for the deuterated entities. A significant positive H/D isotope effect was found for the undissociated peroxide, while for the anions the effect was negligible or slightly in the opposite direction. In addition, for concentrated solutions of peroxide a study of the muon spin polarization as a function of applied transverse magnetic field yielded results consistent with the rate constants determined from the direct decay measurements, and indicated that the reaction products are diamagnetic, most likely MuH and MuOH, i. e., no muoniated radical products are formed. These results are potentially relevant for management of the radiolysis products in nuclear industry. 相似文献
14.
In this work, we consider a frustrated two-leg spin-1/2 ladder composed of Heisenberg ferromagnetic and antiferromagnetic spin-1/2 chains, and nearest spins from different legs interact via Heisenberg type rung exchange interactions that can be either ferromagnetic or antiferromagnetic in nature. The competing exchange interactions in the system lead to five different quantum phases like ferromagnetic, non-collinear ferrimagnetic (NCF), , antiferromagnetic and dimer phases. The quantum phase diagram is constructed for the Heisenberg spin-1/2 model and the phases are characterized using the correlation functions which are calculated by the density matrix renormalization group method. We also analyze the stability of phase and calculate the pitch angle in the NCF phase. 相似文献
15.
Dr. Pablo del Mazo-Sevillano Dr. Alfredo Aguado Dr. Alexandre Zanchet Dr. Octavio Roncero 《Chemphyschem》2023,24(15):e202300291
The (H CO) +OH and H CO-OH+H CO reaction dynamics are studied theoretically for temperatures below 300 K. For this purpose, a full dimension potential energy surface is built, which reproduces well accurate ab initio calculations. The potential presents a submerged reaction barrier, as an example of the catalytic effect induced by the presence of the third molecule. However, quasi-classical and ring polymer molecular dynamics calculations show that the dominant channel is the dimer-exchange mechanism below 200 K, and that the reactive rate constant tends to stabilize at low temperatures, because the effective dipole of either dimer is reduced with respect to that of formaldehyde alone. The reaction complex formed at low temperatures does not live long enough to produce complete energy relaxation, as assumed in statistical theories. These results show that the reactivity of the dimers cannot explain the large rate constants measured at temperatures below 100 K. 相似文献
16.
Molecular platforms are regarded as promising candidates in the generation of units of information for quantum computing. Herein, a strategy combining spin-crossover metal ions and radical ligands is proposed from a model Hamiltonian first restricted to exchange interactions. Unusual spin states structures emerge from the linkage of a singlet/triplet commutable metal centre with two doublet-radical ligands. The ground state nature is modulated by charge transfers and can exhibit a mixture of triplet and singlet local metal spin states. Besides, the superposition reaches a maximum for , suggesting a necessary competition between the intramolecular and inter-metal-ligand and direct exchange interactions. The results promote spinmerism, an original manifestation of quantum entanglement between the spin states of a metal centre and radical ligands. The study provides insights into spin-coupled compounds and inspiration for the development of molecular spin-qubits. 相似文献
17.
Andreas B. Schmidt Jakob Wörner Dr. Andrey Pravdivtsev Stephan Knecht Dr. Harald Scherer Prof. Stefan Weber Prof. Jürgen Hennig Dr. Dominik von Elverfeldt Prof. Jan-Bernd Hövener 《Chemphyschem》2019,20(19):2408-2412
Molecular hydrogen has unique nuclear spin properties. Its nuclear spin isomer, parahydrogen (pH2), was instrumental in the early days of quantum mechanics and allows to boost the NMR signal by several orders of magnitude. pH2-induced polarization (PHIP) is based on the survival of pH2 spin order in solution, yet its lifetime has not been investigated in aqueous or biological media required for in vivo applications. Herein, we report longitudinal relaxation times (T1) and lifetimes of pH2 ( ) in methanol and water, with or without O2, NaCl, rhodium-catalyst or human blood. Furthermore, we present a relaxation model that uses T1 and for more precise theoretical predictions of the H2 spin state in PHIP experiments. All measured T1 values were in the range of 1.4–2 s and values were of the order of 10–300 minutes. These relatively long lifetimes hold great promise for emerging in vivo implementations and applications of PHIP. 相似文献
18.
Dr. Leopold Talirz Dr. Hajo Söde Dr. Shigeki Kawai Dr. Pascal Ruffieux Prof. Ernst Meyer Prof. Dr. Xinliang Feng Prof. Dr. Klaus Müllen Prof. Dr. Roman Fasel Prof. Dr. Carlo A. Pignedoli Daniele Passerone 《Chemphyschem》2019,20(18):2348-2353
We study the band gap of finite armchair graphene nanoribbons (7-AGNRs) on Au(111) through scanning tunneling microscopy/spectroscopy combined with density functional theory calculations. The band gap of 7-AGNRs with lengths of 8 nm and more is converged to within 50 meV of its bulk value of , while the band gap opens by several hundred meV in very short 7-AGNRs. We demonstrate that even an atomic defect, such as the addition of one hydrogen atom at the termini, has a significant effect – in this case, lowering the band gap. The effect can be captured in terms of a simple analytical model by introducing an effective “electronic length”. 相似文献
19.
Dr. Israel P. Assunção Dr. Albano N. Carneiro Neto Prof. Renaldo T. Moura Jr. Dr. Cássio C. S. Pedroso Dr. Ivan G. N. Silva Prof. Maria C. F. C. Felinto Prof. Ercules E. S. Teotonio Prof. Oscar L. Malta Prof. Hermi F. Brito 《Chemphyschem》2019,20(15):1931-1940
The odd–even effect in luminescent [Eu2(L)3(H2O)x]⋅y(H2O) complexes with aliphatic dicarboxylate ligands (L: OXA, MAL, SUC, GLU, ADP, PIM, SUB, AZL, SEB, UND, and DOD, where x=2–6 and y=0–4), prepared by the precipitation method, was observed for the first time in lanthanide compounds. The final dehydration temperatures of the Eu3+ complexes show a zigzag pattern as a function of the carbon chain length of the dicarboxylate ligands, leading to the so-called odd-even effect. The FTIR data confirm the ligand–metal coordination via the mixed mode of bridge–chelate coordination, except for the Eu3+-oxalate complex. XRD results indicate that the highly crystalline materials belong to the monoclinic system. The odd–even effect on the 4 f–4 f luminescence intensity parameters (Ω2 and Ω4) is explained by using an extension of the dynamic coupling mechanism, herein named the ghost-atom model. In this method, the long-range polarizabilities ( ) were simulated by a ghost atom located at the middle of each ligand chain. The values of were estimated using the localized molecular orbital approach. The emission intrinsic quantum yield ( ) of the Eu3+ complexes also presented an the odd-even effect, successfully explained in terms of the zigzag behavior shown by the Ω2 and Ω4 intensity parameters. Luminescence quenching due to water molecules in the first coordination sphere is also discussed and rationalized. 相似文献
20.
Dr. Matko Mužević Assoc. Prof. Dr. Igor Lukačević Ivan Kovač Dr. Davor Gracin Andreja Žužić Prof. Dr. Jelena Macan Asst. Prof. Dr. Maja Varga Pajtler 《Chemphyschem》2023,24(9):e202200837
Inorganic perovskite CaMnO was proposed as a substitution for the TiO anatase in electron transport layers of solar cells containing the hybrid perovskite CH NH PbI based on increased mobility of electrons and better optical matching. Due to a suitable band gap concerning the absorption of sunlight, we investigate the potential of CaMnO and similar manganite perovskites, where Ca is replaced by either Sr, Ba or La, as an absorber layer in inorganic perovskite solar cells. In this study, we have used optical measurements on the synthesized AMnO (A=Ca, Sr, Ba, La) samples to aid density functional theory calculations (DFT) in order to accurately simulate the electronic and optical properties of AMnO compounds and gauge their potential for the role of absorber layer. Both experimental measurements and theoretical calculations show suitable band gap of 1.1-1.5 eV, depending on the compound, and absorption coefficients of the order of cm in the visible part of the spectrum. 相似文献