Anion Ground State Research Articles

Quantum Chemical Study of the Low-Lying Electronic States of VSi3(-/0) Clusters and Interpretation of the Anion Photoelectron Spectrum.

The geometrical and electronic structures of VSi3(-/0) clusters have been investigated with the DFT, CCSD(T), and CASSCF/CASPT2 methods. The results showed that the suitable functional to identify the ground states of VSi3(-/0) clusters is not the B3LYP but the BP86. At the BP86, CCSD(T), and CASPT2 levels, the ground state of the anionic cluster was the (1)A' ((1)A1) of tetrahedral η(3)-(Si3)V(-) isomer, while that of the neutral cluster was the 1(2)A' and 1(2)A″ (1(2)E) of the same isomer. The 1(2)A' and 1(2)A″ of the tetrahedral η(3)-(Si3)V isomer were the results of the Jahn-Teller distortions of the 1(2)E in C3v symmetry. All three bands in the photoelectron spectrum of the VSi3(-) cluster were interpreted by one-electron detachments from the (1)A' anionic ground state on the basis of the BP86, CCSD(T), and CASPT2 methods. The calculated adiabatic and vertical detachment energies were in agreement with the experimental values. The broad shape of the first band was explained by Franck-Condon factor simulations for the (1)A' → 1(2)A' and (1)A' → 1(2)A″ transitions within the tetrahedral η(3)-(Si3)V(-/0) isomers.

Photoelectron imaging spectroscopy of niobium mononitride anion NbN(.).

In this gas-phase photoelectron spectroscopy study, we present the electron binding energy spectrum and photoelectron angular distributions of NbN(-) by the velocity-map imaging technique. The electron binding energy of NbN(-) is measured to be 1.42 ± 0.02 eV from the X band maximum which defines the 0-0 transition between ground states of anion and neutral. Theoretical binding energies which are the vertical and adiabatic detachment energies are computed by density functional theory to compare them with experiment. The ground state of NbN(-) is assigned to the (2)Δ3/2 state and then the electronic transitions originating from this state into X(3)ΔΩ (Ω = 1-3), a(1)Δ2, A(3)Σ1 (-), and b(1)Σ0 (+) states of NbN are reported to interpret the spectral features. As a prospective study for catalytic materials, spectral features of NbN(-) are compared with those of isovalent ZrO(-) and Pd(-).

Theoretical Study of the SinMgm Clusters and Their Cations: Toward Silicon Nanowires with Magnesium Linkers

We investigated the structures of the singly and doubly magnesium-doped silicon clusters in both neutral and cationic states, SinMgm0/+, with n = 1–10 and m = 1 and 2. Total atomization energies (TAEs), heats of formation (ΔHf), and binding energies (Ebs) were determined using the composite G4 method. The Ebs of the Mg-doped clusters are decreased with respect to those of the pure Si counterparts, irrespective of the charge state. As no experimental values are actually available for these systems, the predicted thermochemical values can be used with an expected error margin of ±3 kcal/mol (±0.15 eV or ±12 kJ/mol), due to the uncertainty on the experimental heat of formation of the silicon atom and of the method used. The growth sequence of the singly doped neutral SinMg is similar to that of the singly doped neutral SinLi clusters. In SinMg structures, the Mg atom tends to favor addition on either an edge or a face of the anionic ground-state structure Sin– framework. Only in Si8Mg, Mg substitutes a Si at...

Nonequilibrium spin crossover in copper phthalocyanine

We demonstrate the tip induced control of the spin state of copper phthalocyanine (CuPc) on an insulator coated substrate. Accounting for electronic correlations, we find that, under the condition of energetic proximity of neutral excited states to the anionic groundstate, the system can undergo a population inversion towards these excited states. The resulting state of the system is accompanied by a change in the total spin quantum number. Experimental signatures of the crossover are the appearance of additional nodal planes in the topographical STM images as well as a strong suppression of the current near the center of the molecule. The robustness of the effect against moderate charge conserving relaxation processes has also been tested.

Insights into the geometries, electronic and magnetic properties of neutral and charged palladium clusters.

We performed an unbiased structure search for low-lying energetic minima of neutral and charged palladium PdnQ (n = 2–20, Q = 0, + 1 and –1) clusters using CALYPSO method in combination with density functional theory (DFT) calculations. The main candidates for the lowest energy neutral, cationic and anionic clusters are identified, and several new candidate structures for the cationic and anionic ground states are obtained. It is found that the ground state structures of small palladium clusters are more sensitive to the charge states. For the medium size Pdn0/+/– (n = 16–20) clusters, a fcc-like growth behavior is found. The structural transition from bilayer-like structures to cage-like structures is likely to occur at n = 14 for the neutral and cationic clusters. In contrast, for the anionic counterparts, the structural transition occurs at Pd13–. The photoelectron spectra (PES) of palladium clusters are simulated based on the time-dependent density functional theory (TD-DFT) method and compared with the experimental data. The good agreement between the experimental PES and simulated spectra provides us unequivocal structural information to fully solve the global minimum structures, allowing for new molecular insights into the chemical interactions in the Pd cages.

Photochemical processes induced by the irradiation of 4-hydroxybenzophenone in different solvents.

The singlet and triplet excited states of 4-hydroxybenzophenone (4BPOH) undergo deprotonation in the presence of water to produce the anionic ground-state, causing fluorescence quenching and photoactivity inhibition. The same process does not take place in an aprotic solvent such as acetonitrile. In acetonitrile, 4BPOH is fluorescent (interestingly, one of its fluorescence peaks overlaps with peak C of humic substances), it yields singlet oxygen upon irradiation and induces the triplet-sensitised transformation of phenol (with a rate constant of (6.6 ± 0.3) × 10(7) M(-1) s(-1) (μ ± σ) between phenol itself and a triplet 4BPOH). The 4BPOH shows an intermediate behaviour in a partially protic solvent such as 2-propanol, where some deprotonation of the excited states is observed. In acetonitrile/2-propanol mixtures (at least up to 50% of 2-propanol) there is also some evidence of alcohol oxidation by the 4BPOH triplet state, while the experimental data are silent concerning such a possibility in pure 2-propanol. Considering that benzophenones are important components of chromophoric dissolved organic matter (CDOM) in surface waters, the present findings could have significance for the photoactivity of the hydrophilic surface layers vs. the hydrophobic cores of CDOM.

Photoelectron spectrum of PrO(-).

The photoelectron (PE) spectrum of PrO(-) exhibits a short 835 ± 20 cm(-1) vibrational progression of doublets (210 ± 30 cm(-1) splitting) assigned to transitions from the 4f(2) [(3)H4] σ6s (2) Ω = 4 anion ground state to the 4f(2) [(3)H4] σ6s Ω = 3.5 and 4.5 neutral states. This assignment is analogous to that of the recently reported PE spectrum of CeO(-), though the 82 cm(-1) splitting between the 4f [(2)F2.5] σ6s Ω = 2 and Ω = 3 CeO neutral states could not be resolved [Ray et al., J. Chem. Phys. 142, 064305 (2015)]. The origin of the transition to the Ω = 3.5 neutral ground state is 0.96 ± 0.01 eV, which is the adiabatic electron affinity of PrO. Density functional theory calculations on the anion and neutral molecules support the assignment. The appearance of multiple, irregularly spaced and low-intensity features observed ca. 1 eV above the ground state cannot be reconciled with low-lying electronic states of PrO that are accessible via one-electron detachment. However, neutral states correlated with the 4f(2) [(3)H4] 5d superconfiguration are predicted to be approximately 1 eV above the 4f(2) [(3)H4] σ6s Ω = 3.5 neutral ground state, leading to the assignment of these features to shake-up transitions to the excited neutral states. Based on tentative hot band transition assignments, the term energy of the previously unobserved 4f(2) [(3)H4] σ6s Ω = 2.5 neutral state is determined to be 1840 ± 110 cm(-1).

Parent Anions of Iron, Manganese, and Nickel Tetraphenyl Porphyrins: Photoelectron Spectroscopy and Computations.

The singly charged, parent anions of three transition metal, tetraphenyl porphyrins, M(TPP) [Fe(TPP), Mn(TPP), and Ni(TPP)], were studied by negative ion photoelectron spectroscopy. The observed (vertical) transitions from the ground state anions of these porphyrins to the various electronic states of their neutral counterparts were modeled by density functional theory computations. Our experimental and theoretical results were in good agreement.

Low-lying electronic structure of EuH, EuOH, and EuO neutrals and anions determined by anion photoelectron spectroscopy and DFT calculations.

The anion photoelectron (PE) spectra of EuH(-) and the PE spectrum of overlapping EuOH(-) and EuO(-) anions are presented and analyzed with supporting results from density functional theory calculations on the various anions and neutrals. Results point to ionically bound, high-spin species. EuH and EuOH anions and neutrals exhibit analogous electronic structures: Transitions from (8)Σ(-) anion ground states arising from the 4f(7)σ(6s)(2) superconfiguration to the close-lying neutral (9)Σ(-) and (7)Σ(-) states arising from the 4f(7)σ(6s) superconfiguration are observed spaced by an energy interval similar to the free Eu(+) [4f(7)6s] (9)S - (7)S splitting. The electron affinities (EAs) of EuH and EuOH are determined to be 0.771 ± 0.009 eV and 0.700 ± 0.011 eV, respectively. Analysis of spectroscopic features attributed to EuO(-) photodetachment is complicated by the likely presence of two energetically competitive electronic states of EuO(-) populating the ion beam. However, based on the calculated relative energies of the close-lying anion states arising from the 4f(7)σ(6s) and 4f(6)σ(6s)(2) configurations and the relative energies of the one-electron accessible 4f(7) and 4f(6)σ(6s) neutral states based on ligand-field theory [M. Dulick, E. Murad, and R. F. Barrow, J. Chem. Phys. 85, 385 (1986)], the remaining features are consistent with the 4f(6)σ(6s)(2) (7)Σ(-) and 4f(7)σ(6s) (7)Σ(-) anion states lying very close in energy (the former was calculated to be 0.15 eV lower in energy than the latter), though the true anion ground state and neutral EA could not be established unambiguously. Calculations on the various EuO anion and neutral states suggest 4f-orbital overlap with 2p orbitals in species with 4f(6) occupancy.

All-electron segmented contraction basis sets of triple zeta valence quality for the fifth-row elements

All-electron contracted Gaussian basis set of triple zeta valence quality plus polarisation functions (TZP) for the elements Cs, Ba, La, and from Hf to Rn is presented. Douglas–Kroll–Hess (DKH) basis set for fifth-row elements is also reported. We have recontracted the original TZP basis set, i.e., the values of the contraction coefficients are re-optimised using the second-order DKH Hamiltonian. By addition of diffuse functions (s, p, d, f, and g symmetries), which are optimised for the anion ground states, an augmented TZP basis set is constructed. Using the B3LYP hybrid functional, the performance of the TZP–DKH basis set is assessed for predicting atomic ionisation energy as well as spectroscopy constants of some compounds. Despite its compact size, this set demonstrates consistent, efficient, and reliable performance and will be especially useful in calculations of molecular properties that require explicit treatment of the core electrons.

On the multi-reference character of the low-lying states of the MnS−/0 clusters by the NEVPT2 assignment of the anion photoelectron spectrum

Low-lying electronic states of the MnS−/0 clusters have been investigated by DFT, RCCSD(T), and NEVPT2 methods. The anionic ground state is predicted to be 7Σ+ while the neutral ground state is confirmed as 6Σ+. The 7Σ+→6Σ+ transition is proposed to be at the origin of the lowest energy band of the anion photoelectron spectrum. The 7Σ+→6Π transition is demonstrated to be responsible for the higher energy band. The Franck–Condon factor simulations for these two ionizations, as based on the NEVPT2 potential energy curves, confirm the experimental broadness of the two bands.

On the formation of anions: frequency-, angle-, and time-resolved photoelectron imaging of the menadione radical anion.

Frequency-, angle-, and time-resolved photoelectron imaging of gas-phase menadione (vitamin K3) radical anions was used to show that quasi-bound resonances of the anion can act as efficient doorway states to produce metastable ground electronic state anions on a sub-picosecond timescale. Several anion resonances have been experimentally observed and identified with the assistance of ab initio calculations, and ground state anion recovery was observed across the first 3 eV above threshold. Time-resolved measurements revealed the mechanism of electronic ground state anion formation, which first involves a cascade of very fast internal conversion processes to a bound electronic state that, in turn, decays by slower internal conversion to the ground state. Autodetachment processes from populated resonances are inefficient compared with electronic relaxation through internal conversion. The mechanistic understanding gained provides insight into the formation of radical anions in biological and astrochemical systems.

Internal conversion outcompetes autodetachment from resonances in the deprotonated tetracene anion continuum.

Photoelectron velocity-map imaging and electronic structure calculations have been used to study the temporary anion (resonance) dynamics of the closed-shell site-specific deprotonated tetracene anion (C18H11(-)) in the hv = 3.26 eV (380 nm) to 4.13 eV (300 nm) range. In accord with a recent frequency-, angle-, and time-resolved photoelectron imaging study on a related but open-shell polyaromatic radical anion (Chem. Sci., 2015, 6, 1578-1589), population of π*-resonances situated in the detachment continuum efficiently recover the ground electronic state of the anion through ultrafast non-adiabatic dynamics, followed by characteristic statistical electron loss (thermionic emission). The combined electron yield of direct photodetachment and autodetachment from the optically-accessed resonances in C18H11(-) is several orders of magnitude smaller than thermionic emission from the ground electronic electronic state in the photon energy range studied. This result implies a resilience to prompt photoejection from UV radiation, and the ability of neutral PAH-like species to capture a free electron and form a long-lived molecular anion that ultimately decays by thermionic emission on a millisecond timescale. The attachment mechanism applies to polyaromatic species that cannot support dipole-bound states, and may provide an additional route to forming anions in astrochemical environments.

High resolution photoelectron imaging of UO(-) and UO2(-) and the low-lying electronic states and vibrational frequencies of UO and UO2.

We report a study of the electronic and vibrational structures of the gaseous uranium monoxide and dioxide molecules using high-resolution photoelectron imaging. Vibrationally resolved photoelectron spectra are obtained for both UO(-) and UO2(-). The spectra for UO2(-) are consistent with, but much better resolved than a recent study using a magnetic-bottle photoelectron analyzer [W. L. Li et al., J. Chem. Phys. 140, 094306 (2014)]. The electron affinity (EA) of UO is reported for the first time as 1.1407(7) eV, whereas a much more accurate EA is obtained for UO2 as 1.1688(6) eV. The symmetric stretching modes for the neutral and anionic ground states, and two neutral excited states for UO2 are observed, as well as the bending mode for the neutral ground state. These vibrational frequencies are consistent with previous experimental and theoretical results. The stretching vibrational modes for the ground state and one excited state are observed for UO. The current results for UO and UO2 are compared with previous theoretical calculations including relativistic effects and spin-orbit coupling. The accurate experimental data reported here provide more stringent tests for future theoretical methods for actinide-containing species.

Photodetachment cross sections of theC2nH− (n=1–3)hydrocarbon-chain anions

We report theoretical results of the low-energy photodetachment cross sections of the ${\mathrm{C}}_{2}\mathrm{H}{}^{\ensuremath{-}},\phantom{\rule{0.16em}{0ex}}{\mathrm{C}}_{4}\mathrm{H}{}^{\ensuremath{-}}$, and ${\mathrm{C}}_{6}\mathrm{H}{}^{\ensuremath{-}}$ hydrocarbon-chain anions. The complex Kohn variational technique is used to calculate molecular-frame transition dipole moments from the anion ground state to a photoelectron in the continuum of the neutral radical. We employ the Franck-Condon approximation and include interchannel electronic coupling to determine the low-energy photodetachment cross sections and asymmetry parameters. We discuss the behavior of the cross section, especially near thresholds, and describe the role of electronic resonances and excited channels. The theoretical results reproduce the main characteristics of recent measurements of absolute photodetachment cross sections.

Elucidating the Electronic Structures of the Ground States of the VO2(-/0) Clusters: Synergism between Computation and Experiment.

Electronic structures of VO2 and its anion were investigated with density functional theory (DFT), complete active space second-order perturbation theory (CASPT2), and restricted coupled-cluster with single, double, and perturbative triple excitations (RCCSD(T)) computational quantum chemical methods. The results show that there is a near-degeneracy of the lowest (3)B1, (3)A1, and (1)A1 states of the anion. Therefore, the 532 and 193 nm photoelectron spectra of VO2(-) are interpreted by exploring these states as possible initial states. The anionic ground state was identified at the highest computational level, that is, RCCSD(T), as (3)B1 allowing the X band to be assigned to the (3)B1 → (2)B1 transition, while the lower intensity and lower binding energy X' and X″ features are ascribed to the (1)A1 → (2)A1 and (3)A1 → (2)A1 ionizations, respectively. The latter assignment is different from the recently proposed assignment of the corresponding slow electron velocity-map imaging (SEVI) spectra. Further, the A band is suggested to be mainly the result of an ionization from (3)B1 to 2(2)A1. For all these ionizations an electron is removed from a predominant metal orbital. The higher energy bands B and C on the contrary can be ascribed as electron detachments out of molecular orbitals largely located on the oxygen centers. More precisely, the B band is attributed to the ionizations from (3)B1 to (4)A2 and (2)A2, while the C band is proposed to originate from the (3)B1 → (4)B1 and (3)B1 → 2(2)B1 ionizations. The proposed novel assignment is further corroborated by calculating the Franck-Condon factors, which largely agree with the experimental vibrational progressions of the SEVI spectra.

Full-dimensional diabatic potential energy surfaces including dissociation: The 2E″ state of NO3

A scheme to produce accurate full-dimensional coupled diabatic potential energy surfaces including dissociative regions and suitable for dynamical calculations is proposed. The scheme is successfully applied to model the two-sheeted surface of the (2)E″ state of the NO3 radical. An accurate potential energy surface for the NO₃⁻ anion ground state is developed as well. Both surfaces are based on high-level ab initio calculations. The model consists of a diabatic potential matrix, which is expanded to higher order in terms of symmetry polynomials of symmetry coordinates. The choice of coordinates is key for the accuracy of the obtained potential energy surfaces and is discussed in detail. A second central aspect is the generation of reference data to fit the expansion coefficients of the model for which a stochastic approach is proposed. A third ingredient is a new and simple scheme to handle problematic regions of the potential energy surfaces, resulting from the massive undersampling by the reference data unavoidable for high-dimensional problems. The final analytical diabatic surfaces are used to compute the lowest vibrational levels of NO₃⁻ and the photo-electron detachment spectrum of NO₃⁻ leading to the neutral radical in the (2)E″ state by full dimensional multi-surface wave-packet propagation for NO3 performed using the Multi-Configuration Time Dependent Hartree method. The achieved agreement of the simulations with available experimental data demonstrates the power of the proposed scheme and the high quality of the obtained potential energy surfaces.

7-Hydroxyflavone Revisited: Spectral, Acid–Base Properties, and Interplay of the Protolytic Forms in the Ground and Excited States

Spectral and acid-base properties of 7-hydroxyflavone (7HF) in the ground and excited states were investigated with a purpose to enable reasonable application of this dye and its derivatives as fluorescent probes. Analysis of solvatochromic and solvatofluorochromic ability of 7HF in 20 solvents, investigations of 7HF spectral properties in the frozen solvents, spectrophotometric and spectrofluorimetric titrations in methanol-water (4:1 v/v) in the wide pH/H0 range (from pH = 11.0 to H0 = -4.5), analysis of the 3D fluorescence and time-resolved spectra, as well as quantum-chemical calculations were carried out. It has been found that 7HF can exist in three protolythic forms-neutral, anion, and cation-depending on the environment acidity or basicity. In the excited state, in methanol-water solutions, there are four forms: neutral, cation and anion, which can be formed by direct excitation of the ground-state anion or by photodissociation of the neutral form depending on pH, and only one phototautomer, which appears in the H0 range from 1.3 to -4.5. It has been shown that the mechanism of the phototautomer formation depends on medium acidity. The photoautomer can be formed by cation photodissociation as well as by photoanion protonation. Finally, it was concluded which of the 7HF protolytic forms can be used for fluorescent probing.

Measurement of the electron affinity of atomic Ce

Photoelectron spectra of Ce${}^{\ensuremath{-}}$ obtained using both 2.33- and 3.49-eV photon energies resolve numerous transitions between the ${}^{4}{H}_{7/2}$ ($\ensuremath{\cdots}$4$f$ 5${d}^{2}$ 6${s}^{2}$) anion ground state and excited neutral states, in addition to transitions from excited anion states to the ground and excited neutral states. Building on the theoretical work of O'Malley and Beck [S. M. O'Malley and D. R. Beck, Phys. Rev. A 74, 042509 (2006)] and the known term energies of Ce excited states, we determined the adiabatic electron affinity of Ce to be 0.570(20) eV, which is lower than previously reported experimental values. The term energy of the lowest-energy excited anion state arising from the $\ensuremath{\cdots}$4$f$ 5$d$ 6${s}^{2}$ 6$p$ configuration was also determined to be 0.210(20) eV.

Probing the electronic structure and Au–C chemical bonding in AuC2− and AuC2 using high-resolution photoelectron spectroscopy

We report photoelectron spectroscopy (PES) and high-resolution PE imaging of AuC2(-) at a wide range of photon energies. The ground state of AuC2(-) is found to be linear (C∞v, (1)Σ(+)) with a …8π(4)4δ(4)17σ(2)9π(4)18σ(2) valence configuration. Detachments from all the five valence orbitals of the ground state of AuC2(-) are observed at 193 nm. High-resolution PE images are obtained in the energy range from 830 to 330 nm, revealing complicated vibronic structures from electron detachment of the 18σ, 9π, and 17σ orbitals. Detachment from the 18σ orbital results in the (2)Σ(+) ground state of neutral AuC2, which, however, is bent due to strong vibronic coupling with the nearby (2)Π state from detachment of a 9π electron. The (2)Σ(+)-(2)Π vibronic and spin-orbit coupling results in complicated vibronic structures for the (2)Σ(+) and (2)Π3/2 states with extensive bending excitations. The electron affinity of AuC2 is measured accurately to be 3.2192(7) eV with a ground state bending frequency of 195(6) cm(-1). The first excited state ((2)A') of AuC2, corresponding to the (2)Π3/2 state at the linear geometry, is only 0.0021 eV above the ground state ((2)A') and has a bending frequency of 207(6) cm(-1). The (2)Π1/2 state, 0.2291 eV above the ground state, is linear with little geometry change relative to the anion ground state. The detachment of the 17σ orbital also results in complicated vibronic structures, suggesting again a bent state due to possible vibronic coupling with the lower (2)Π state. The spectrum at 193 nm shows the presence of a minor species with less than 2% intensity relative to the ground state of AuC2(-). High-resolution data of the minor species reveal several vibrational progressions in the Au-C stretching mode, which are assigned to be from the metastable (3)Π2,1,0 spin-orbit excited states of AuC2(-) to the (2)Π3/2,1/2 spin-orbit states of neutral AuC2. The spin-orbit splittings of the (3)Π and (2)Π states are accurately measured at the linear geometry. The current study provides a wealth of electronic structure information about AuC2(-) and AuC2, which are ideal systems to investigate the strong Σ-Π and spin-orbit vibronic couplings.