Electron Detachment Research Articles

Reactivity of Polynuclear Niobium Oxynitride Cluster Anions Nb4N5-xOx - (x=0-5) toward N2.

The activation of N₂ under mild conditions remains a significant challenge in chemistry. Understanding how the composition of ligands modulates the reactivity of metal centers is pivotal for the rational design of efficient catalysts for nitrogen fixation. Herein, the reactions between polynuclear niobium oxynitride anions Nb4N5-xOx - (x=0-5) and N2 were investigated by employing mass spectrometry, photoelectron imaging spectroscopy, and theoretical calculations. The rate constants of Nb4N5-xOx -/N2 gradually decrease for x=0 to x=4, and then increase again for x=5. The sharp increase of the rate constants of Nb4O5 -/N2 corresponds to a decrease in the electron detachment energy of the Nb4O5 - cluster in the photoelectron spectroscopic experiments. Theoretical calculations suggest that the low-coordinated Nb-Nb sites in Nb4N5-xOx - (x=0-5) behaves as the active centers to bind N2 in the side-on/end-on manner. Mechanistic analysis reveals that reducing the N/O ratio leads to higher electron densities on the active Nb-Nb centers and decreased positive charge on the metal atoms, which hinders the approach of N2 to the clusters. This finding discloses fundamental insights into the impact of N/O ratio in fine-tuning the reactivity of metal centers toward N2 adsorption in related catalytic processes.

Streamer inception probability in air at atmospheric pressure – an experimental and theoretical analysis

Abstract We consider a self-consistent and probabilistic formulation of the classical Raether–Meek streamer inception model, and compare it with dedicated experiments. Our approach is based on the statistical evaluation of a first critical electron. This is done by evaluating the Raether–Meek integral for arbitrary starting positions of the first electron, and evaluating the size of the region in which the electrons can transition into a streamer. Then, using an ensemble-averaged model for the negative ion distribution which acts as a source of initial electrons, we compute the time-dependent probability of streamer inception. Unlike the standard Meek-based inception model, the experiments show that the generalized formulation is valid for both voltage polarities, but in return it requires knowledge about the initial ion distribution and electron detachment rate.

Generation of seed electrons in guided ionization waves in He–O2 mixtures: The effect of negative ion cluster formation

The kinetics of electrons and negative ions was numerically studied under the conditions, which are typical for multi-pulsed guided ionization waves in He flows ejected into ambient air. It was shown that, in He with a small admixture of O2 or air, O2− ions formed due to three-body electron attachment in the discharge afterglow are rapidly converted to O4− cluster ions in pulse off time. We suggested that seed electrons are generated at the leading edge of a pulse in two steps, and these steps are dissociation of O4− ions to form O2− ions followed by electron detachment from the O2− ions. The rate of O4− dissociation was calculated in He–O2 mixtures for various reduced electric fields on the basis of a Monte Carlo simulation. This rate, as well as the rate of electron detachment from O2− ions calculated previously, was used to simulate seed electron generation in a high-voltage nanosecond pulse in He–O2 mixtures for different gas pressures. It was shown that the formation of O4− ions drastically hinders the generation of seed electrons in multi-pulsed guided ionization waves in He–O2 and He–air mixtures.

Strongly bound anions featuring bismuth fluoride building blocks

The stability of polynuclear superhalogen anions composed of BiF5 building blocks was investigated using ab initio electronic structure methods and flexible basis sets. A comprehensive exploration of the ground state potential energy surfaces of (Bi2F11)−, (Bi3F16)− and (Bi4F21)− anions, which can be viewed as comprising BiF5 fragments and an additional fluorine atom, led to the identification of their isomeric structures. It was found that the most stable isomers, predicted to dominate at room temperature, correspond to chain-like extended structures containing BiF6 subunits, with fluorine ligands arranged octahedrally around Bi atoms, sharing F atoms to form Bi–F–Bi bridging linkages. The vertical electron detachment energies of the (BinF5n+1)− anions (n = 1–4) were found to be very high (ranging from 10.91 to 13.36 eV) and increased with the number of bismuth atoms (n) and thus the BiF5 building blocks involved in the structure. Thermodynamic stability of the (BinF5n+1)− anions (i.e., their susceptibility to fragmentation) was also verified and discussed.

Fourth-Order Algebraic Diagrammatic Construction for Electron Detachment and Attachment: The IP- and EA-ADC(4) Methods.

We present a non-Dyson fourth-order algebraic diagrammatic construction formulation of the electron propagator, featuring the distinct IP- and EA-ADC(4) schemes for the treatment of ionization and electron attachment processes. The algebraic expressions have been derived automatically using the intermediate state representation approach and implemented in the Q-Chem quantum-chemical program package. The performance of the novel methods is assessed with respect to high-level reference data for ionization potentials and electron affinities of closed- and open-shell systems. While only minor improvements over the corresponding third-order methods are observed for one-hole ionization and one-particle electron attachment processes from closed-shell systems (MAEIP-ADC(4) = 0.27 eV and MAEEA-ADC(4) = 0.05 eV), a significantly enhanced performance is found in case of open-shell reference states (MAEIP-ADC(4) = 0.11 eV and MAEEA-ADC(4) = 0.02 eV). A particularly appealing feature of the novel methods is their accurate treatment of satellite transitions. For closed-shell reference states, we obtain accuracies of MAEIP-ADC(4) = 0.81 eV and MAEEA-ADC(4) = 0.27 eV, while in case of open-shell reference states, mean absolute errors of MAEIP-ADC(4) = 0.15 eV and MAEEA-ADC(4) = 0.27 eV are found.

Observation of a core-excited dipole-bound state ∼1eV above the electron detachment threshold in cryogenically cooled acetylacetonate.

Dipole-bound states in anions exist when a polar neutral core binds an electron in a diffuse orbital through charge-dipole interaction. Electronically excited polar neutral cores can also bind an electron in a diffuse orbital to form Core-Excited Dipole-Bound States (CE-DBSs), which are difficult to observe because they usually lie above the electron detachment threshold, leading to very short lifetimes and, thus, unstructured transitions. We report here the photodetachment spectroscopy of cryogenically cooled acetylacetonate anion (C5H7O2-) recorded by detecting the neutral radical produced upon photodetachment and the infrared spectroscopy in He-nanodroplets. Two DBSs were identified in this anion. One of them lies close to the electron detachment threshold (∼2.74eV) and is associated with the ground state of the radical (D0-DBS). Surprisingly, the other DBS appears as resonant transitions at 3.69eV and is assigned to the CE-DBS associated with the first excited state of the radical (D1-DBS). It is proposed that the resonant transitions of the D1-DBS are observed ∼1eV above the detachment threshold because its lifetime is determined by the internal conversion to the D0-DBS, after which the fast electron detachment takes place.

Multiple differential electron spectra from detachment in collisions of 30–300-keV anions with atoms and molecules

We have measured triple differential momentum distributions for electron detachment in collisions of 30- and 300-keV anions (C− and Si−) with atoms and molecules (He, Ar, and N2). The entire angular range of the ejected electrons was covered. The binary encounter ring, well known from positive ion-atom collisions, was observed in most cases. In a quasifree-electron scattering model this structure represents elastic scattering of the active electron from the target. However, especially for the slowest projectiles, this model fails to reproduce the angular distributions. In this regime it is probably necessary to use quasimolecular models to describe the collision. Indications for a projectile cusp are observed, implying that excitation-induced dipole moments in the ion projectile may be important. Published by the American Physical Society 2024

Electron Binding Energies of Open-Shell Species from Diagonal Electron-Propagator Self-Energies with Unrestricted Hartree-Fock Spin-Orbitals.

For closed-shell molecules, valence electron binding energies may be calculated accurately and efficiently with ab initio electron-propagator methods that have surpassed their predecessors. Advantageous combinations of accuracy and efficiency range from cubically scaling methods with mean errors of 0.2 eV to quintically scaling methods with mean errors of 0.1 eV or less. The diagonal self-energy approximation in the canonical Hartree-Fock basis is responsible for the enhanced efficiency of several methods. This work examines the predictive capabilities of diagonal self-energy approximations when they are generalized to the canonical spin-orbital basis of unrestricted Hartree-Fock (UHF) theory. Experimental data on atomic electron binding energies and high-level, correlated calculations in a fixed basis for a set of open-shell molecules constitute standards of comparison. A review of the underlying theory and analysis of numerical errors lead to several recommendations for the calculation of electron binding energies: (1) In calculations that employ the diagonal self-energy approximation, Koopmans's identity for UHF must be qualitatively correct. (2) Closed-shell reference states are preferable to open-shell reference states in calculations of molecular ionization energies and electron affinities. (3) For molecular electron binding energies between doublets and triplets, calculations of electron detachment energies are more accurate and efficient than calculations of electron attachment energies. When these recommendations are followed, mean absolute errors increase by approximately 0.05 eV with respect to their counterparts obtained with closed-shell reference orbitals.

Model two states dynamics of photo‐detachment [F‐H‐F]− induced by an optimally designed polychromatic field

AbstractPhoto‐detachment of electron from [F‐H‐F] to generate neutral [F‐H‐F] has been studied in this article. Neutral has a linear structure and this is the transition state (T.S.) of F + HF FH + F reaction. The Potential Energy Surface (P.E.S.) of neutral [F‐H‐F] and molecular anion [F‐H‐F] for the asymmetric stretching mode is generated and the dynamics under the influence of an external polychromatic field is followed. The P.E.S. of [F‐H‐F] looks like a “flat‐bed” single well where as for [F‐H‐F] it has a symmetrical double well structure. In absence of any external field these two surfaces are well separated. But in presence of external field transition from molecular anion [F‐H‐F] to neutral molecule [F‐H‐F] takes place which causes the detachment of an electron. We have designed an optimal designed field using Simulated Annealing and studied the dynamics of electron detachment by such external fields. We have achieved detachment probability of by applying the optically designed field.

Cyanonaphthalene and cyanonaphthyl radicals: Vibrational structures via computed negative ion photoelectron spectra and thermochemistry of 1- and 2-cyanonaphthalene.

A double harmonic oscillator model is applied to compute the negative ion photoelectron spectra (NIPES) of the 1- and 2-cyanonaphthalene (CNN) radical anions. The computed Franck-Condon factors utilize optimized structures and harmonic vibrational frequencies obtained using density functional theory with the B3LYP 6-311++G (2d,2p) basis set while considering the mode-mixing Duschinsky effects. To test the accuracy of our model, the NIPES of α and β naphthyl radical anions were computed, and a strong agreement between the slow electron velocity-map ion imaging spectra and the predicted spectra was found. The adiabatic electron affinities (EAs) of the ground singlet states (S0) in 1-CNN and 2-CNN are 0.856 and 0.798eV, respectively. The origin of the lowest-lying triplet (T1) states in 1-CNN and 2-CNN is found to be 3.226 and 3.266eV, resulting in singlet-triplet energy splittings (ΔEST) of 2.370 and 2.468eV, respectively. Both the NIPES for electron detachment to the S0 and T1 states exhibit well-resolved vibrational features, allowing for the assignment of several vibrational fundamental frequencies. Following deprotonation, several isomers are formed, with the most stable deprotonated radical anions in 1-CNN and 2-CNN, corresponding to the removal of the most acidic proton, with EAs of 2.062 and 2.16eV. The rich spectroscopic and thermochemical data obtained in the current study make the CNN radical anions and their deprotonated species interesting systems for investigation in gas-phase, negative-ion experiments.

Observation of the Transition from Triple Bonds to Single Bonds between Ru-Ge Bonding in RuGeO(CO)n- (n = 3-5).

This work reports the observation and characterization of heterobinuclear transition-metal main-group metal oxide carbonyl complex anions, RuGeO(CO)n- (n = 3-5), by combining mass-selected photoelectron velocity map imaging spectroscopy and quantum chemistry calculations. The experimentally determined vertical electron detachment energy of RuGeO(CO)3- surpasses those of RuGeO(CO)4- and RuGeO(CO)5-, which is attributed to distinctive bonding features. RuGeO(CO)3- manifests one covalent σ and two Ru-to-Ge dative π bonds, contrasting with the sole covalent σ bond present in RuGeO(CO)4- and RuGeO(CO)5-. Unpaired spin density distribution analysis reveals a 17-electron configuration at the Ru center in RuGeO(CO)3- and an 18-electron configuration in RuGeO(CO)4- and RuGeO(CO)5-. This work closes a gap in the quantitative physicochemical characterization of heteronuclear oxide carbonyl complexes, enhancing our insights into catalytic processes of CO/GeO on the metal surface at the molecular level.

The detachment-induced mode in electronegative capacitively coupled radio-frequency plasmas

Insights into the spatio-temporally resolved electron power absorption dynamics in capacitively coupled radio-frequency plasmas are essential for understanding the fundamentals of their operation and as a basis for knowledge-based plasma process development. Similar to the γ-mode, an ionization maximum is observed at the sheath edge around the time of maximum sheath voltage in electronegative oxygen discharges at a pressure of 300 Pa. Based on Particle-in-Cell/Monte Carlo Collisions (PIC/MCC) simulations, we demonstrate that this maximum is not only caused by secondary electrons emitted at the electrode and collisionally multiplied inside the sheath. In fact, it also occurs in the complete absence of secondary electrons in the simulation, and is caused by the generation of O− ions by electron attachment close to the electrode during the local sheath collapse. These negative ions are accelerated towards the plasma bulk by the sheath electric field during sheath expansion. By electron detachment from these negative ions, electrons are generated inside the sheath and are accelerated towards the plasma bulk by the instantaneous sheath electric field—similarly to secondary electrons. Ionization is also observed in the plasma bulk and caused by electrons generated by detachment and accelerated by the high drift-and ambipolar electric fields. This detachment-induced electron power absorption is found to have significant effects on the discharge in the presence and absence of secondary electron emission. Its fundamentals are understood based on an analysis of the spatio-temporal electron and O− power absorption dynamics as well as the trajectory of selected O− ions close to the electrode.

Synthesis of N2-Type Superatomic Molecules.

Exploration of multiple bonds between superatoms remains an uncharted territory. In this study, we present the synthesis and characterization of N2-type superatomic molecules featuring triple bonds between two superatoms. The successful synthesis of M2Au17 (M = Pd, Pt) nanoclusters hinged upon the photoinduced fusion of MAu12 superatoms, achieved through sequential electron transfer and detachment of [AuPR3]+ species. Solid-state structures were confirmed via X-ray crystallography, while their electronic structures were elucidated through density functional theory (DFT) calculations. Analysis of electronic absorption properties, coupled with time-dependent DFT calculations, unveiled a symmetry-dependent electron transition nature between superatomic molecular orbitals, akin to that observed in conventional molecules.

Ab Initio Electron Propagators with an Hermitian, Intermediately Normalized Superoperator Metric Applied to Vertical Electron Affinities.

New-generation ab initio electron propagator methods for calculating electron detachment energies of closed-shell molecules and anions have surpassed their predecessors' accuracy and computational efficiency. Derived from an Hermitian, intermediately normalized superoperator metric, these methods contain no adjustable parameters. To assess their versatility, a standard set (NIST-50-EA) of 50 vertical electron affinities of small closed-shell molecules based on NIST reference data has been created. Errors with respect to reference data on 23 large, conjugated organic photovoltaic (OPV23) molecules have also been analyzed. All final states are valence anions that correspond to electron affinities between 0.2 and 4.2 eV. For a given scaling of the arithmetic bottleneck, the new-generation methods obtain the lowest mean absolute errors (MAEs). The best methods with fifth-power arithmetic scaling realize MAEs below 0.1 eV. Composite models comprising cubically and quintically scaling calculations executed with large and small basis sets, respectively, produce OPV23 MAEs near 0.05 eV. The accuracy of quintically scaling methods executed with large basis sets is thereby procured with reduced computational effort. New-generation results obtained with and without the diagonal self-energy approximation in the canonical Hartree-Fock basis have been compared. These results indicate that Dyson orbitals closely resemble canonical Hartree-Fock orbitals multiplied by the square root of a probability factor above 0.85.

Benchmarking Ionization Potentials from pCCD Tailored Coupled Cluster Models.

The ionization potential (IP) is an important parameter providing essential insights into the reactivity of chemical systems. IPs are also crucial for designing, optimizing, and understanding the functionality of modern technological devices. We recently showed that limiting the CC ansatz to the seniority-zero sector proves insufficient in predicting reliable and accurate ionization potentials within an IP equation-of-motion coupled-cluster formalism. Specifically, the absence of dynamical correlation in the seniority-zero pair coupled cluster doubles (pCCD) model led to unacceptably significant errors of approximately 1.5 eV. In this work, we aim to explore the impact of dynamical correlation and the choice of the molecular orbital basis (canonical vs localized) in CC-type methods targeting 230 ionized states in 70 molecules, comprising small organic molecules, medium-sized organic acceptors, and nucleobases. We focus on pCCD-based approaches as well as the conventional IP-EOM-CCD and IP-EOM-CCSD. Their performance is compared to the CCSD(T) or CCSDT equivalent and experimental reference data. Our statistical analysis reveals that all investigated frozen-pair coupled cluster methods exhibit similar performance, with differences in errors typically within chemical accuracy (1 kcal/mol or 0.05 eV). Notably, the effect of the molecular orbital basis, such as canonical Hartree-Fock or natural pCCD-optimized orbitals, on the IPs is marginal if dynamical correlation is accounted for. Our study suggests that triple excitations are crucial in achieving chemical accuracy in IPs when modeling electron detachment processes with pCCD-based methods.

Electronic Control of the Position of the Pb Atom on the Surface of B8 Borozene in the PbB8 Cluster.

Spontaneous symmetry-breaking is common in chemical and physical systems. Here, we show that by adding an electron to the C7v PbB8 cluster, which consists of a planar B8 disk with the Pb atom situated along the C7 axis, the Pb atom spontaneously moves to the off-axis position in the PbB8- anion. Photoelectron spectroscopy of PbB8- reveals a broad ground-state transition and a large energy gap, suggesting a highly stable closed-shell PbB8 borozene complex and a significant geometry change upon electron detachment. Quantum chemistry calculations indicate that the lowest unoccupied molecular orbital of the C7v PbB8 cluster is a degenerate π orbital mainly consisting of the Pb 6px and 6py atomic orbitals. Occupation of one of the 6p orbitals spontaneously break the C7v symmetry in the anion due to the Jahn-Teller effect. The large amplitude of the position change of Pb in PbB8- relative to PbB8 is surprising owing to bonding interactions between the Pb 6p orbital with the π orbital of the B8 borozene.

Structural evolution and bonding properties of Nb1-2Gen-/0 (n = 3-7) clusters: Anion photoelectron spectroscopy and theoretical calculations.

This study presents a collaborative experimental and theoretical investigation into the structures and electronic properties of niobium-doped germanium clusters. Anion photoelectron spectra for Nb1-2Gen- (n = 3-7) clusters were acquired using 266nm photon energies, enabling the determination of adiabatic detachment energies and vertical detachment energies. In conjunction with these experimental measurements, density functional theory (DFT) calculations were conducted to validate the experimentally obtained electron detachment energies and elucidate the geometric and electronic structures of each anionic cluster. The agreement between DFT calculations and experimental data establishes a solid foundation for assessing the structural evolution and electronic properties of niobium-doped germanium clusters. It is noted that both neutral and anionic clusters exhibit predominantly similar overall structural characteristics, with the exception of Nb2Ge6- and Nb2Ge6. Furthermore, this investigation emphasizes the exceptional chemical stability of the D3d symmetric chair-shaped structure in Nb2Ge6-, providing insights into its bonding characteristics.

Searching for the Achilles' Heel of Urethane Linkage-An Energetic Perspective.

A sudden increase in polyurethane (PU) production necessitates viable recycling methods for the waste generated. PU is one of the most important plastic materials with a wide range of applications; however, the stability of the urethane linkage is a major issue in chemical recycling. In this work, termination reactions of a model urethane molecule, namely methyl N-phenyl carbamate (MPCate), are investigated using G3MP2B3 composite quantum chemical method. Our main goal was to gain insights into the energetic profile of urethane bond termination and find an applicable chemical recycling method. Hydrogenation, hydrolysis, methanolysis, peroxidation, glycolysis, ammonolysis, reduction with methylamine and termination by dimethyl phosphite were explored in both gas and condensed phases. Out of these chemicals, degradation by H2, H2O2 and CH3NH2 revealed promising results with lower activation barriers and exergonic pathways, especially in water solvation. Implementing these effective PU recycling methods can also have significant economic benefits since the obtained products from the reactions are industrially relevant substances. For example, aniline and dimethyl carbonate could be reusable in polymer technologies serving as potential methods for circular economy. As further potential transformations, several ionizations of MPCate were also examined including electron capture and detachment, protonation/deprotonation and reaction with OH-. Alkaline digestion against the model urethane MPCate was found to be promising due to the relatively low activation energy. In an ideal case, the transformation of the urethane bond could be an enzymatic process; therefore, potential enzymes, such as lipoxygenase, were also considered for the catalysis of peroxidation, and lipases for methanolysis.

Characterizing Precipitation Behaviors of H− in the Martian Atmosphere

AbstractSolar wind protons can charge exchange with the extensive hydrogen corona of Mars, resulting in a significant flux of energetic neutral atoms (ENAs). As these solar wind hydrogen ENAs precipitate into the upper atmosphere, they can experience electron attachment or detachment, resulting in populations of H− and H+, respectively, with upstream velocity. We seek to characterize the behavior of H− in the ionosphere of Mars through a combination of in situ data analysis and mathematical models. Observations indicate that measurable H− precipitation in the ionosphere of Mars is rare, occurring during only 1.8% of available observations. These events occur primarily during high energy solar wind conditions near perihelion. We also compare H− fluxes to those of H+ and find that H− fluxes are ∼4.5 times less than H+, indicating preferential conversion of hydrogen ENAs to H+. We develop a simple model describing the evolution of the charged and neutral fraction of ENAs and H− ions versus altitude. We find that 0.29%–0.78% of ENAs are converted to H− for solar wind energies 1–3 keV. We also predict that the effects of photodetachment on the H‐H− system are non‐negligible.

Influence of external electric field on properties of Cyclotriparaphenyl[6]carbon

Cyclotriparaphenyl[6]carbon is a hypothetical derivative compound of cyclo[12]carbon, in which three CC triple bonds are replaced by three benzene rings. Comprehensive investigations of influence of external electric field (EEF) on cyclotriparaphenyl[6]carbon have been performed from theoretical aspect in this work. The maximum appropriate applied electric field strength is 0.0265 a.u., electron detachment will occur when EEF exceeds this value. When the EEF is in the range of 0–0.0265 a.u., with the increase of EEF, the shape of cyclotriparaphenyl[6]carbon turns from a circle to oval, the HOMO-LUMO gap gradually decreases from 6.046 eV at 0 a.u. to 2.322 eV at 0.0265 a.u., and its absorption band extends to VL (visible light) region and near-infrared region little by little. When the EEF are 0.025 a.u. and 0.0265 a.u., its maximum absorption wavelengths are 1220.6 nm and 1383.5 nm, respectively. HOMA (Harmonic oscillator measure of aromaticity), AV1245 and electron localization function (ELF) calculation results indicate that cyclotriparaphenyl[6]carbon has no aromaticity in the EEF range of 0–0.0265 a.u.. The compound exhibitspromising potential forapplication inthefield of colordevelopingcompound materials.