Comment on: “Probing the Properties of Polynuclear Superhalogens without Halogen Ligand via ab Initio Calculations: A Case Study on Double‐Bridged [Mg2(CN)5]−1 Anions” by Li et al.

Díaz–Tinoco, Manuel; Ortiz, J. V.

doi:10.1002/cphc.201600519

Cited by 10 publications

(4 citation statements)

References 11 publications

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“…Progress in EP methodology has been recorded in many reviews − ,− and two books. , Predictive capabilities of these techniques have been evaluated, and recommendations for computational practitioners have been published recently . With programs that perform these calculations being available to many users for over two decades, applications to VEDEs of anions also have been widespread. ,,,,− …”

Section: Introductionmentioning

confidence: 99%

Electron Propagator Methods for Vertical Electron Detachment Energies of Anions: Benchmarks and Case Studies

Díaz–Tinoco

Corzo

Ortiz

2018

J. Chem. Theory Comput.

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Ab initio electron propagator methods are efficient and accurate means of calculating vertical electron detachment energies of closed-shell, molecular anions with nuclei from the first three periods. Basis set extrapolations enable definitive comparisons between electron propagator results and benchmarks defined by total energy differences obtained with coupled-cluster, single, double, plus perturbative triple substitution theory. The best compromises of accuracy and efficiency are provided by the renormalized, partial third-order, diagonal (P3+) self-energy and by the nondiagonal, renormalized, second-order (NR2) approximation. The outer-valence Green function, the two-particle-one-hole Tamm− Dancoff approximation, the third-order algebraic diagrammatic construction, and the renormalized third-order methods also are examined. A detailed analysis of errors for small anions is performed. Case studies include F − (H 2 O) and Cl − (H 2 O) complexes, C 5 H 5 − , two P 2 N 3 − pentagonal rings, and a superhalide, Al(BO 2 ) 4 − , whose electron detachment energy is more than double those of the halide anions. These applications illustrate the versatility of electron propagator methods, their utility for interpreting negative-ion photoelectron spectra, and their promise in the discovery of unusual properties and patterns of chemical bonding. Composite methods, which combine basis set effects calculated at the relatively efficient diagonal, second-order level and higher correlation effects calculated with small basis sets, provide excellent estimates of basis setextrapolated P3+ or NR2 results and facilitate applications to large molecules. In the P3+ and NR2 methods, a judicious choice of low-order couplings between hole operators that correspond to the assumptions of Koopmans's theorem and operators that describe final-state relaxation and polarization and initial-state correlation leads to predictive accuracy, computational efficiency, and interpretive lucidity.

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Section: Introductionmentioning

confidence: 99%

Electron Propagator Methods for Vertical Electron Detachment Energies of Anions: Benchmarks and Case Studies

Díaz–Tinoco

Corzo

Ortiz

2018

J. Chem. Theory Comput.

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“…It should also be noticed that the much higher VDEs of several binuclear and polynuclear superhalogen anions with CN ligands − result due to Koopmans’ defects. In such cases, the symmetry of the final state does not correspond to the HOMO of the initial state, i.e., the ground state of the doublet.…”

Section: Resultsmentioning

confidence: 99%

M(BO)_k+1^– Anions: Novel Superhalogens Based on Boronyl Ligands

Srivastava

2022

J. Phys. Chem. A

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Superhalogens have been a subject of continuous attraction in the last four decades due to their unusual structures and interesting applications. In the quest for new superhalogens based on boronyl (BO) ligands, we investigate M(BO) k+1 – anions using a high-level ab initio CCSD(T) and B3LYP density functional method for M = Li, Na, K, Be, Mg, Ca, B, and Al. Their structures are linear for M = Li, Na, K; trigonal planar for M = Be, Mg, Ca; and tetrahedral for M = B, Al. These anions are energetically and thermodynamically stable against various fragmentations. Their superhalogen property has been established due to their higher vertical detachment energy (VDE) than halogen, being in the range 4.44–7.81 eV. For a given k, the stability and VDE of M(BO) k+1 – anions decrease with an increase in the size of M, which is due to the decrease in charge delocalization on BO moieties. There exists a linear correlation between frontier orbitals energy gap and VDE with coefficient R 2 = 0.93888. It was also noticed that the BO ligand, due to the lower dimerization energy, can be preferably used as an inorganic analogue of CN. However, the structural relaxation in BO-based neutral species significantly affect the VDE and, hence, their superhalogen nature. We believe that these findings should be interesting for researchers working in superatomic chemistry as well as in boron chemistry.

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“…Metal (M with m valence electrons) halide (X) anions with the general formula M i X mi +1 – that exhibit delocalization of Dyson orbitals over many halogen centers have been especially frequent objects of study. − Extensions to alternative electronegative ligands have been shown to be feasible. − Even organic ligands such as carboxylates and amino acids or fluoroborate tripods were discovered to be suitable for constructing superhalogens. − Connections between the search for more powerful superhalogens with record-setting electron detachment energies and the optimization of superacids with superlative Brønsted acidity have been identified after analysis of electron propagator calculations on icosahedral carboranes. , OF 3 – turns out to be a superhalogen, as do large H n F n +1 – clusters with extraordinarily large electron detachment energies, alkali-metal complexes with borane, HF–MF n – clusters, boron–nitrogen fluoride oligomers, NaCl clusters, noble-gas fluorides, BO 2 – , and (by a narrow margin) BS 2 – . Direct calculation of improvements to canonical Hartree–Fock energies has proven to be a crucial advantage in superhalide clusters where the qualifying electron detachment energy does not correspond to the highest occupied molecular orbital. − For example, in clusters with CN ligands, the order of σ and π orbitals may be reversed by electron correlation.…”

Section: Introductionmentioning

confidence: 99%

Electron Propagator Theory of Vertical Electron Detachment Energies of Anions: Benchmarks and Applications to Nucleotides

2023

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A new generation of ab initio electron-propagator self-energy approximations that are free of adjustable parameters is tested on a benchmark set of 55 vertical electron detachment energies of closed-shell anions. Comparisons with older self-energy approximations indicate that several new methods that make the diagonal self-energy approximation in the canonical Hartree−Fock orbital basis provide superior accuracy and computational efficiency. These methods and their acronyms, mean absolute errors (in eV), and arithmetic bottlenecks expressed in terms of occupied (O) and virtual (V) orbitals are the opposite-spin, non-Dyson, diagonal second-order method (os-nD-D2, 0.2, OV 2 ), the approximately renormalized quasiparticle third-order method (Q3+, 0.15, O 2 V 3 ) and the approximately renormalized, non-Dyson, linear, third-order method (nD-L3+, 0.1, OV 4 ). The Brueckner doubles with triple field operators (BD-T1) nondiagonal electron-propagator method provides such close agreement with coupled-cluster single, double, and perturbative triple replacement total energy differences that it may be used as an alternative means of obtaining standard data. The new methods with diagonal self-energy matrices are the foundation of a composite procedure for estimating basis-set effects. This model produces accurate predictions and clear interpretations based on Dyson orbitals for the photoelectron spectra of the nucleotides found in DNA.

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Comment on: “Probing the Properties of Polynuclear Superhalogens without Halogen Ligand via ab Initio Calculations: A Case Study on Double‐Bridged [Mg₂(CN)₅]⁻¹ Anions” by Li et al.

Cited by 10 publications

References 11 publications

Electron Propagator Methods for Vertical Electron Detachment Energies of Anions: Benchmarks and Case Studies

Electron Propagator Methods for Vertical Electron Detachment Energies of Anions: Benchmarks and Case Studies

M(BO)_k+1^– Anions: Novel Superhalogens Based on Boronyl Ligands

Electron Propagator Theory of Vertical Electron Detachment Energies of Anions: Benchmarks and Applications to Nucleotides

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Comment on: “Probing the Properties of Polynuclear Superhalogens without Halogen Ligand via ab Initio Calculations: A Case Study on Double‐Bridged [Mg2(CN)5]−1 Anions” by Li et al.

Cited by 10 publications

References 11 publications

Electron Propagator Methods for Vertical Electron Detachment Energies of Anions: Benchmarks and Case Studies

Electron Propagator Methods for Vertical Electron Detachment Energies of Anions: Benchmarks and Case Studies

M(BO)k+1– Anions: Novel Superhalogens Based on Boronyl Ligands

Electron Propagator Theory of Vertical Electron Detachment Energies of Anions: Benchmarks and Applications to Nucleotides

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Comment on: “Probing the Properties of Polynuclear Superhalogens without Halogen Ligand via ab Initio Calculations: A Case Study on Double‐Bridged [Mg₂(CN)₅]⁻¹ Anions” by Li et al.

M(BO)_k+1^– Anions: Novel Superhalogens Based on Boronyl Ligands