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We report the x-ray absorption spectrum (XAS) of the tert-butyl radical, C4H9. The radical was generated pyrolytically from azo-tert-butane, and the XAS of the pure radical was obtained by subtraction of spectra recorded at different temperatures. The bands in the XAS were assigned by ab initio calculations that are in very good agreement with the experimental data. The lowest energy signal in the XAS is assigned to the C1s electron transition from the central carbon atom to the singly occupied molecular orbital (SOMO), while higher transitions correspond to C1s excitations from terminal carbon atoms. Furthermore, we investigated the fragmentation of the radical following resonant C1s excitation by electron-ion-coincidence spectroscopy. Several fragmentation channels were identified. The C1s excitation of the terminal carbons is associated with a stronger fragmentation tendency compared to the lowest C1s excitation of the central carbon into the SOMO. For this core excited state, we still observe an intact parent ion, C4H9+, and a comparatively higher tendency to dissociate into CH3+ + C3H6+.
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We report the photoelectron spectrum of the pyridyl radical (C5H4N), a species of interest in astrochemistry and combustion. The radicals were produced via hydrogen abstraction in a fluorine discharge and ionized with synchrotron radiation. Mass-selected slow photoelectron spectra of the products were obtained from photoelectron-photoion coincidence spectra. A Franck-Condon simulation based on computed geometries and vibrational frequencies identified contributions of the o- and p-pyridyl radicals. For the o-isomer an adiabatic ionisation energy of 7.70 eV was obtained, in excellent agreement with a computed value of 7.72 eV. The spectrum of o-pyridyl is characterized by a long progression in an in-plane bending mode and the N-C stretch that contains the radical site.
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We present experiments on reservoir computing (RC) using a network of vertical-cavity surface-emitting lasers (VCSELs) that we diffractively couple via an external cavity. Our optical reservoir computer consists of 24 physical VCSEL nodes. We evaluate the system's memory and solve the 2-bit XOR task and the 3-bit header recognition (HR) task with bit error ratios (BERs) below 1% and the 2-bit digital-to-analog conversion (DAC) task with a root mean square error (RMSE) of 0.067.
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Substituting CC with the isoelectronic BN units is a promising approach to modify the optoelectronic properties of polycyclic aromatic hydrocarbons. While computational studies have already addressed trends in the electronic structure of the various isosteres, experimental data are still scarce. Here, the excited state spectroscopy and dynamics of 4a,8a-azaboranaphthalene were studied by picosecond time-resolved photoionization in a supersonic jet and analyzed with the aid of XMS-CASPT2 and time-dependent DFT calculations. A resonance-enhanced multiphoton ionization spectrum (REMPI) reveals the S1 origin at î¡ = 33 830 ± 12 cm-1. Several vibrational bands were resolved and assigned by comparison with the computations. A [1+1] photoelectron spectrum via the S1 origin yielded an adiabatic ionization energy of 8.27 eV. Selected vibrational bands were subsequently investigated by pump-probe photoionization. While the origin as well as several low-lying vibronic states exhibit lifetimes in the ns-range, a monoexponential decay is observed at higher excitation energies, ranging from 400 ps at +1710 cm-1 to 13 ps at +3360 cm-1. The deactivation is attributed to an internal conversion of the optically excited S1 state via a barrier that gives access to a conical intersection (CI) to the S0 state. The doping significantly changes the energetic ordering of CIs and lowers the corresponding energy barrier for the associated deactivation pathway, as revealed by nudged elastic band (NEB) calculations.
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The fragmentation of fulminic acid, HCNO, after excitation and ionization of core electrons was investigated using Auger-electron-photoion coincidence spectroscopy. A considerable degree of site-selectivity is observed. Ionization of the carbon and oxygen 1s electron leads to around 70% CH+ + NO+, while ionization at the central N-atom produces only 37% CH+ + NO+, but preferentially forms O+ + HCN+ and O+ + CN+. The mass-selected Auger-electron spectra show that these fragments are associated with higher binding energy final states. Furthermore, ionization of the C 1s electron leads to a higher propensity for C-H bond fission compared to O 1s ionization. Following resonant Auger-Meitner decay after 1s â 3π excitation, 12 different ionic products are formed. At the C 1s edge, the parent ion HCNO+ is significantly more stable compared to the other two edges, which we also attribute to the higher contribution of final states with low binding energies in the C 1s resonant Auger electron spectra.
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Nonlinear dynamical systems exhibiting inherent memory can process temporal information by exploiting their responses to input drives. Reservoir computing is a prominent approach to leverage this ability for time-series forecasting. The computational capabilities of analog computing systems often depend on both the dynamical regime of the system and the input drive. Most studies have focused on systems exhibiting a stable fixed-point solution in the absence of input. Here, we go beyond that limitation, investigating the computational capabilities of a paradigmatic delay system in three different dynamical regimes. The system we chose has an Ikeda-type nonlinearity and exhibits fixed point, bistable, and limit-cycle dynamics in the absence of input. When driving the system, new input-driven dynamics emerge from the autonomous ones featuring characteristic properties. Here, we show that it is feasible to attain consistent responses across all three regimes, which is an essential prerequisite for the successful execution of the tasks. Furthermore, we demonstrate that we can exploit all three regimes in two time-series forecasting tasks, showcasing the versatility of this paradigmatic delay system in an analog computing context. In all tasks, the lowest prediction errors were obtained in the regime that exhibits limit-cycle dynamics in the undriven reservoir. To gain further insights, we analyzed the diverse time-distributed node responses generated in the three regimes of the undriven system. An increase in the effective dimensionality of the reservoir response is shown to affect the prediction error, as also fine-tuning of the distribution of nonlinear responses. Finally, we demonstrate that a trade-off between prediction accuracy and computational speed is possible in our continuous delay systems. Our results not only provide valuable insights into the computational capabilities of complex dynamical systems but also open a new perspective on enhancing the potential of analog computing systems implemented on various hardware platforms.
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A scalable straightforward synthesis of monofluoro- and difluoromethyl triflate CF3 SO2 OCH2 F (MH2F ) and CF3 SO2 OCHF2 (MHF2 ) through electrochemical fluorination (ECF, Simons process) of methyl triflate MH3 in anhydrous hydrogen fluoride at nickel anodes is presented. The ECF method is also feasible for the preparation of the deuterated analogues CF3 SO2 OCD2 F (MD2F ) and CF3 SO2 OCDF2 (MD2F ). Surprisingly, no H/D exchange occurs during ECF of CF3 SO2 OCD3 (MD3 ); this provides further evidence for a NiF3 /NiF4 -mediated ECF mechanism. The ECF of selected partially fluorinated ethyl triflates is described, and electrochemical fluorination of CF3 SO2 OCH2 CF3 (EH2F3 ) leads to the until now unknown chiral CF3 SO2 OCHFCF3 (EHFF3 ). The analogous fluoromethyl and fluoroethyl nonaflates are also accessible by ECF. This study contains detailed spectroscopic, structural, and thermal data on (fluoro)methyl and fluoro(ethyl) triflates.
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The electronic structure of biradicals is characterized by the presence of two unpaired electrons in degenerate or near-degenerate molecular orbitals. In particular, some of the most relevant species are highly reactive, difficult to generate cleanly and can only be studied in the gas phase or in matrices. Unveiling their electronic structure is, however, of paramount interest to understand their chemistry. Photoelectron photoion coincidence (PEPICO) spectroscopy is an excellent approach to explore the electronic states of biradicals, because it enables a direct correlation between the detected ions and electrons. This permits to extract unique vibrationally resolved photoion mass-selected threshold photoelectron spectra (ms-TPES) to obtain insight in the electronic structure of both the neutral and the cation. In this review we highlight most recent advances on the spectroscopy of biradicals and biradicaloids, utilizing PEPICO spectroscopy and vacuum ultraviolet (VUV) synchrotron radiation.
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Time delay reservoir computing (TDRC) using semiconductor lasers (SLs) has proven to be a promising photonic analog approach for information processing. One appealing property is that SLs subject to delayed optical feedback and external optical injection, allow for tuning the response bandwidth by changing the level of optical injection. Here we use strong optical injection, thereby expanding the SL's modulation response up to tens of gigahertz. Performing a nonlinear time series prediction task, we demonstrate experimentally that for appropriate operating conditions, our TDRC system can operate with sampling times as small as 11.72 ps, without sacrificing computational performance.
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We report a joint experimental and computational study of the photoelectron spectroscopy and the dissociative photoionization of fulminic acid, HCNO. The molecule is of interest to astrochemistry and astrobiology as a potential precursor of prebiotic molecules. Synchrotron radiation was used as the photon source. Dispersive photoelectron spectra were recorded from 10 to 22 eV, covering four band systems in the HCNO cation, and an ionization energy of 10.83 eV was determined. Transitions into the Renner-Teller distorted X+2Π state of the cation were simulated using wavepacket dynamics based on a vibronic coupling Hamiltonian. Very good agreement between experiment and theory is obtained. While the first excited state of the cation shows only a broad and unstructured spectrum, the next two higher states exhibit a well-resolved vibrational progression. Transitions into the excited electronic states of HCNO+ were not simulated due to the large number of electronic states that contribute to these transitions. Nevertheless, a qualitative assignment is given, based on the character of the orbitals involved in the transitions. The dissociative photoionization was investigated by photoelectron-photoion coincidence spectroscopy. The breakdown diagram shows evidence for isomerization from HCNO+ to HNCO+ on the cationic potential energy surface. Zero Kelvin appearance energies for the daughter ions HCO+ and NCO+ have been derived.
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Networks of semiconductor lasers are the foundation of numerous applications and fundamental investigations in nonlinear dynamics, material processing, lighting, and information processing. However, making the usually narrowband semiconductor lasers within the network interact requires both high spectral homogeneity and a fitting coupling concept. Here, we report how we use diffractive optics in an external cavity to experimentally couple vertical-cavity surface-emitting lasers (VCSELs) in a 5×5 array. Out of the 25 lasers, we succeed to spectrally align 22, all of which we lock simultaneously to an external drive laser. Furthermore, we show the considerable coupling interactions between the lasers of the array. This way, we present the largest network of optically coupled semiconductor lasers reported so far and the first detailed characterization of such a diffractively coupled system. Due to the high homogeneity of the lasers, the strong interaction between them, and the scalability of the coupling approach, our VCSEL network is a promising platform for experimental investigations of complex systems, and it has direct applications as a photonic neural network.
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We investigated the excited-state dynamics of 4-(dimethylamino)benzethyne (4-DMABE) in a combined theoretical and experimental study using surface-hopping simulations and time-resolved ionisation experiments. The simulations predict a decay of the initially excited S2 state into the S1 state in only a few femtoseconds, inducing a subsequent partial twist of the dimethylamino group within â¼100 fs. This leads to drastically reduced Franck-Condon factors for the ionisation transition to the cationic ground state, thus inhibiting the effective ionisation of the molecule, which leads to a vanishing photoelectron signal on a similar timescale as observed in our time-resolved photoelectron spectra. From the phototoelectron spectra, an adiabatic ionisation energy of 7.17 ± 0.02 eV was determined. The experimental decays match the theoretical predictions very well and the combination of both reveals the electronic characteristics of the molecule, namely the role of intramolecular charge transfer (ICT) states in the deactivation pathway of electronically excited 4-DMABE.
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Methyl and methylene compounds of arsenic and antimony have been studied by photoelectron photoion coincidence spectroscopy to investigate their relative stability. While for As both HAs=CH2 , As-CH3 and the methylene compound As=CH2 are identified in the spectrum, the only Sb compound observed is Sb-CH3 . Thus, there is a step in the main groupâ 15 between As and Sb, regarding the relative stability of the methyl compounds. Ionisation energies, vibrational frequencies and spin-orbit splittings were determined for the methyl compound from photoion mass-selected photoelectron spectra. Although the spectroscopic results for organoantimony resemble those for the previously investigated bismuth compounds, EPR spectroscopic experiments indicate a far lower tendency for methyl transfer for Sb(CH3 )3 compared to Bi(CH3 )3 . This study concludes investigations on low-valent organopnictogen compounds.
Assuntos
Antimônio , Arsênio , Espectroscopia Fotoeletrônica , Espectrometria de Massas , Antimônio/químicaRESUMO
Trimethylborane (TMB) and its chemistry upon pyrolysis have been investigated by threshold photoelectron spectroscopy. TMB shows an unstructured spectrum and its adiabatic ionization energy (IEad) has been determined to be 9.93 ± 0.1 eV. Dissociative photoionization induces a methyl radical loss in TMB and the barrier to dissociation in the cation is measured to be 0.65 ± 0.1 eV. Upon pyrolysis methane loss dominates, leading to C2H5B, which can exist in five different isomeric structures. Quantum chemical calculations were used to investigate possible methane loss mechanisms as well as the isomerization pathways on the C2H5B potential energy surface. Through isomer-selective photoion mass-selected threshold photoelectron spectroscopy (ms-TPES) the two isomers CH3BCH2 and CH3CHBH were identified by their ms-TPE spectra and IEad values of 8.55 ± 0.02 eV and 8.73 ± 0.02 eV were determined, respectively. A second channel leading to the loss of ethene from TMB forms CH2BH, which exhibits an IEad value of 9.37 ± 0.03 eV. The reaction mechanism in the literature needs to be expanded by an additional methane loss from the intermediately formed ethyl methyl borane.
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Isolated 2-phenylallyl radicals (2-PA), generated by pyrolysis from a nitrite precursor, have been investigated by IR/UV ion dip spectroscopy using free electron laser radiation. 2-PA is a resonance-stabilized radical that is considered to be involved in the formation of polycyclic aromatic hydrocarbons (PAH) in combustion, but also in interstellar space. The radical is identified based on its gas-phase IR spectrum. Furthermore, a number of bimolecular reaction products are identified, showing that the self-reaction as well as reactions with unimolecular decomposition products of 2-PA form several PAH efficiently. Possible mechanisms are discussed and the chemistry of 2-PA is compared with the one of the related 2-methylallyl and phenylpropargyl radicals.
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Reservoir computing is a machine learning approach that can generate a surrogate model of a dynamical system. It can learn the underlying dynamical system using fewer trainable parameters and, hence, smaller training data sets than competing approaches. Recently, a simpler formulation, known as next-generation reservoir computing, removed many algorithm metaparameters and identified a well-performing traditional reservoir computer, thus simplifying training even further. Here, we study a particularly challenging problem of learning a dynamical system that has both disparate time scales and multiple co-existing dynamical states (attractors). We compare the next-generation and traditional reservoir computer using metrics quantifying the geometry of the ground-truth and forecasted attractors. For the studied four-dimensional system, the next-generation reservoir computing approach uses â¼ 1.7 × less training data, requires 10 × shorter "warmup" time, has fewer metaparameters, and has an â¼ 100 × higher accuracy in predicting the co-existing attractor characteristics in comparison to a traditional reservoir computer. Furthermore, we demonstrate that it predicts the basin of attraction with high accuracy. This work lends further support to the superior learning ability of this new machine learning algorithm for dynamical systems.
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We design scalable neural networks adapted to translational symmetries in dynamical systems, capable of inferring untrained high-dimensional dynamics for different system sizes. We train these networks to predict the dynamics of delay-dynamical and spatiotemporal systems for a single size. Then, we drive the networks by their own predictions. We demonstrate that by scaling the size of the trained network, we can predict the complex dynamics for larger or smaller system sizes. Thus, the network learns from a single example and by exploiting symmetry properties infers entire bifurcation diagrams.
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N-Doped polycyclic aromatic hydrocarbons have recently emerged as potential organic electronic materials. The function of such materials is determined not only by the intrinsic electronic properties of individual molecules but also by their supramolecular interactions in the solid state. Therefore, a proper characterization of the interactions between the individual units is of interest to materials science since they ultimately govern properties such as excitons and charge transfer. Here, we report a joint experimental and computational study of two azaphenanthrene dimers to determine the structure and the nature of supramolecular interactions in the aggregates. IR/UV double-resonance experiments were carried out using far- and mid-infrared free-electron laser radiation. The experimental spectra are compared with quantum chemical calculations for the lowest-energy π-stacked and hydrogen-bonded structures. The data reveal a preference of the π-stacked structure for the benzo[f]quinoline and the phenanthridine dimer.
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A series of well-defined cationic hepta-coordinate bismuth halides [BiX2(py)5][B(3,5-(CF3)2-C6H3)4] (X = Cl, Br, I), stabilized only by substitutionally labile solvent molecules, were synthesized and fully characterized. Their apparent D5h symmetry with a lone pair at the central atom is unprecedented for main group compounds. The potential of BiX3 to show unexpectedly high Lewis acidities in moderately polar solvents is likely due to the formation of [BiX2(solv)5]+ and related ionic species.
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HCNO is a molecule of considerable astrochemical interest as a precursor to prebiotic molecules. It is synthesized by preparative pyrolysis and is unstable at room temperature. Here, we investigate its spectroscopy in the soft X-ray regime at the C 1s, N 1s and O 1s edges. All 1s ionization energies are reported and X-ray absorption spectra reveal the transitions from the 1s to the π* state. Resonant and normal Auger electron spectra for the decay of the core hole states are recorded in a hemispherical analyzer. An assignment of the experimental spectra is provided with the aid of theoretical counterparts. The latter are using a valence configuration interaction representation of the intermediate and final state energies and wavefunctions, the one-center approximation for transition rates and band shapes according to the moment theory. The computed spectra are in very good agreement with the experimental data and most of the relevant bands are assigned. Additionally, we present a simple approach to estimate relative Auger transition rates on the basis of a minimal basis representation of the molecular orbitals. We demonstrate that this provides a qualitatively good and reliable estimate for several signals in the normal and resonant Auger electron spectra which have significantly different intensities in the decay of the three core holes.