Electron Propagator Calculations on the Ionization Energies of Nucleic Acid Bases, Base-Water Complexes and Base Dimers

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

doi:10.1007/978-94-010-0113-7_46

Cited by 9 publications

(10 citation statements)

References 30 publications

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“…Ab initio electron-propagator (EP) methods for determining IPs and EAs − have been used extensively in the interpretation of photoelectron spectra of molecules and molecular ions. − A given EP approximation is defined by the form of the self-energy (∑) employed in the Dyson equation. The most widely employed approximations are based on canonical Hartree–Fock (HF) orbitals and their energies, which are used to define the zeroth order EP.…”

Section: Introductionmentioning

confidence: 99%

Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules IV: Electron-Propagator Methods

Dolgounitcheva

Díaz–Tinoco

Zakrzewski

et al. 2016

J. Chem. Theory Comput.

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Comparison of ab initio electron-propagator predictions of vertical ionization potentials and electron affinities of organic, acceptor molecules with benchmark calculations based on the basis set-extrapolated, coupled cluster single, double, and perturbative triple substitution method has enabled identification of self-energy approximations with mean, unsigned errors between 0.1 and 0.2 eV. Among the self-energy approximations that neglect off-diagonal elements in the canonical, Hartree-Fock orbital basis, the P3 method for electron affinities, and the P3+ method for ionization potentials provide the best combination of accuracy and computational efficiency. For approximations that consider the full self-energy matrix, the NR2 methods offer the best performance. The P3+ and NR2 methods successfully identify the correct symmetry label of the lowest cationic state in two cases, naphthalenedione and benzoquinone, where some other methods fail.

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Section: Introductionmentioning

confidence: 99%

Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules IV: Electron-Propagator Methods

Dolgounitcheva

Díaz–Tinoco

Zakrzewski

et al. 2016

J. Chem. Theory Comput.

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“…Pickup and Goscinski laid a foundation for the derivation and interpretation of self-energy approximations by identifying second-order relaxation, polarization, and correlation terms . 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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“…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

191

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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Electron Propagator Calculations on the Ionization Energies of Nucleic Acid Bases, Base-Water Complexes and Base Dimers

Cited by 9 publications

References 30 publications

Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules IV: Electron-Propagator Methods

Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules IV: Electron-Propagator Methods

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

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

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