Ab initio electron propagator calculations on electron detachment energies of nickel phthalocyanine tetrasulfonate tetraanions

Dolgounitcheva, O.; Zakrzewski, V. G.; Ortiz, J. V.

doi:10.1002/qua.23216

Cited by 4 publications

(4 citation statements)

References 29 publications

(61 reference statements)

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“…Even though the electron density of the phthalocyanine framework resides between the Cu atom and the four sulfonates, the Coulomb interaction is best described using a dielectric constant of unity. This system was recently studied theoretically 4 where excellent agreement with the experimental findings described above was obtained.…”

Section: The Coulomb Interactions Produce Repulsive Coulombsupporting

confidence: 60%

Coulomb Potentials Have Strong Effects on Anion Electronic States

Simons

2013

J. Phys. Chem. C

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The Coulomb destabilization of intrinsic electron binding strengths and in forming repulsive Coulomb barriers (RCB) that can act to trap an excess electron are overviewed for a variety of anionic systems that include (i) multiply charged anions in which the charged sites are spatially well separated, (ii) multiply charged anions that have negative electron binding energies but in which the RCB decreases the rate of electron detachment, (iii) multiply charged superhalogen anions, (iv) positively charged polypeptides in which positive sites’ Coulomb potentials stabilize antibonding orbitals allowing an electron to attach, (v) DNA duplex oligomers containing a thymine dimer damage site that is repaired by electron attachment, and (vi) DNA fragments in which an electron attached to a base π* orbital results in formation of a strand break. Special attention is paid to the degree to which such Coulomb interactions are screened, especially in the latter two cases.

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Section: The Coulomb Interactions Produce Repulsive Coulombsupporting

confidence: 60%

Coulomb Potentials Have Strong Effects on Anion Electronic States

Simons

2013

J. Phys. Chem. C

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“…Many applications of ab initio electron propagator methods to neutral and anionic carbon clusters, fullerenes, porphyrins, phthalocyanines, nucleic acid fragments, polycyclic aromatic hydrocarbons, organometallics, and other organic compounds have been reported and reviewed recently by the author and his collaborators 61–93. In collaboration with Martínez and coworkers94–102 and Zein103,104 photoelectron spectra of metal‐oxide clusters anions have been assigned and patterns of electronic structure and reactivity have been analyzed with the aid of Dyson orbitals.…”

Section: Survey Of Recent Applicationsmentioning

confidence: 99%

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry

Ortiz

2012

WIREs Comput Mol Sci

189

194

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Electron propagator theory provides a practical means of calculating electron binding energies, Dyson orbitals, and ground‐state properties from first principles. This approach to ab initio electronic structure theory also facilitates the interpretation of its quantitative predictions in terms of concepts that closely resemble those of one‐electron theories. An explanation of the physical meaning of the electron propagator's poles and residues is followed by a discussion of its couplings to more complicated propagators. These relationships are exploited in superoperator theory and lead to a compact form of the electron propagator that is derived by matrix partitioning. Expressions for reference‐state properties, relationships to the extended Koopmans's theorem technique for evaluating electron binding energies, and connections between Dyson orbitals and transition probabilities follow from this discussion. The inverse form of the Dyson equation for the electron propagator leads to a strategy for obtaining electron binding energies and Dyson orbitals that generalizes the Hartree–Fock equations through the introduction of the self‐energy operator. All relaxation and correlation effects reside in this operator, which has an energy‐dependent, nonlocal form that is systematically improvable. Perturbative arguments produce several, convenient (e.g. partial third order, outer valence Green's function, and second‐order, transition‐operator) approximations for the evaluation of valence ionization energies, electron affinities, and core ionization energies. Renormalized approaches based on Hartree–Fock or approximate Brueckner orbitals are employed when correlation effects become qualitatively important. Reference‐state total energies based on contour integrals in the complex plane and gradients of electron binding energies enable exploration of final‐state potential energy surfaces. © 2012 John Wiley & Sons, Ltd. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods

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“…Early applications to Ni(CN) 4 2– with perturbative methods were followed by examinations of complexes composed of transition metals with halide ligands. , The stability of doubly charged carbon cluster anions with acetylenic features was demonstrated. , Subsequent calculations disclosed the feasibility of extending this structural motif to quadruply charged carbon anions . A substituted Ni phthalocyanine with a metastable −4 charge was examined as well . The introduction of fully relativistic generalizations of electron propagator methods facilitated studies of platinum complexes with halide or cyanide ligands. − Electron binding energies of SiF 6 2– also have been calculated .…”

Section: Introductionmentioning

confidence: 99%

“…58 A substituted Ni phthalocyanine with a metastable −4 charge was examined as well. 59 The introduction of fully relativistic generalizations of electron propagator methods facilitated studies of platinum complexes with halide or cyanide ligands. 60−65 Electron binding energies of SiF 6 2− also have been calculated.…”

Section: ■ Introductionmentioning

confidence: 99%

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

2023

Self Cite

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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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Ab initio electron propagator calculations on electron detachment energies of nickel phthalocyanine tetrasulfonate tetraanions

Cited by 4 publications

References 29 publications

Coulomb Potentials Have Strong Effects on Anion Electronic States

Coulomb Potentials Have Strong Effects on Anion Electronic States

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry

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

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