Natural ionization orbitals for interpreting electron detachment processes

Thompson, Lee M.; Harb, Hassan; Hratchian, Hrant P.

doi:10.1063/1.4951738

Cited by 27 publications

(25 citation statements)

References 57 publications

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“…515253 Electron detachments modeled by DFT calculations were characterized using the natual ionization orbital model. 54 Geometry optimizations were carried out using standard techniques and potential energy surface stationary points were characterized using analytic second-derivative calculations. 45 Reported energies include zero-point energy corrections.…”

Section: Methodsmentioning

confidence: 99%

Photoelectron Spectra of Gd2O2− and Non-Monotonic Photon-Energy Dependent Variations in Populations of Close-Lying Neutral States

Mason¹,

Harb²,

Taka³

et al. 2020

Preprint

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Photoelectron spectra of Gd2O2− obtained with photon energies from 2.033 eV to 3.495 eV exhibit numerous close-lying neutral states with photon-energy-dependent relative intensities. Transitions to states falling within the electron binding energy window of 0.9 and 1.6 eV are attributed to one- or two-electron transitions to the ground and low-lying excited neutral states. An additional, manifold of electronic states observed in the 2.1 to 2.8 eV window cannot be assigned to any simple one-electron transitions. Because of the relatively simple electronic structure from the half-filled 4f7 subshell occupancy in Gd2O2–, the numerous transitions observed in the spectra are fairly well-resolved, allowing a detailed view of the changes in relative intensities of individual transitions with photon energy. With supporting calculations on the numerous close-lying electronic states, we suggest a description of strong photoelectron-valence electron interactions that result in the photon-energy dependent shake-up transitions and switching between ferro- and antiferromagnetic coupling.

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Section: Methodsmentioning

confidence: 99%

Photoelectron Spectra of Gd2O2− and Non-Monotonic Photon-Energy Dependent Variations in Populations of Close-Lying Neutral States

Mason¹,

Harb²,

Taka³

et al. 2020

Preprint

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“…128,129 Franck-Condon (FC) spectra were generated using the implementation by Bloino, Barone, and co-workers. 132 The NIO model provides the Dyson orbital for a ∆SCF treatment of electron detachment and, within the sudden approximation, provides insight to electron relaxation accompanying electron detachment. The NIO model has been successfully employed in a number of recent studies involving similar systems.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…The NIO model has been successfully employed in a number of recent studies involving similar systems. 64,132,133 Results and Discussion were collected only out to ∼10,000 cm −1 ; see Fig. S1 in the SI for the full overview spectrum.…”

Section: Experimental Methodsmentioning

confidence: 99%

Unveiling the Coexistence of Cis and Trans Isomers in the Hydrolysis of ZrO2: A Coupled DFT and High-Resolution Photoelectron Spectroscopy Study

Taka¹,

Babin²,

Sheng³

et al. 2020

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High-resolution anion photoelectron spectroscopy of the ZrO3H2- and ZrO3D2- anions and complementary electronic structure calculations are used to investigate the reaction between zirconium dioxide and a single water molecule, ZrO20/- + H2O. Experimental spectra of ZrO3H2- and ZrO3D2- were obtained using slow photoelectron velocity-map imaging (cryo-SEVI), revealing the presence of two dissociative adduct conformers and yielding insight into the vibronic structure of the corresponding neutral species. Franck-Condon simulations for both the \textit{cis}-- and \textit{trans}--dihydroxide structures are required to fully reproduce the experimental spectrum. Additionally, it was found that water-splitting is stabilized more by ZrO2 than TiO2, suggesting Zr-based catalysts are more reactive toward hydrolysis.

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“…A few years ago, our lab proposed the natural ionization orbital (NIO) model to provide such an interpretive tool initially developed for use with ΔSCF calculations. 82 The NIO model utilizes a natural orbital transformation of the difference density formed from the initial (with N electrons) and final (with N ± 1 electrons) SCF solutions. The NIO model has been instrumental in making photodetachment spectral assignments and developing an orbital description of the ionization process that would not have been correct using the Koopmans' theorem framework.…”

Section: Introductionmentioning

confidence: 99%

∆SCF Dyson Orbitals and Pole Strengths from Natural Ionization Orbitals

Harb¹,

Hratchian

2020

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The calculation of photoionization cross-sections can play a key role in spectral assignments using modeling and simulation. In this work, we provide formal relationships between pole strengths, which are proportional to the photoionization cross-section, and terms related to the Natural Ionization Orbital model for Delta-SCF calculations. A set of numerical calculations using the developed models is carried out. Pole strength values computed using the two approaches developed for Delta-SCF calculations demonstrate excellent agreement with an electron propagator theory model.

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Natural ionization orbitals for interpreting electron detachment processes

Cited by 27 publications

References 57 publications

Photoelectron Spectra of Gd2O2− and Non-Monotonic Photon-Energy Dependent Variations in Populations of Close-Lying Neutral States

Photoelectron Spectra of Gd2O2− and Non-Monotonic Photon-Energy Dependent Variations in Populations of Close-Lying Neutral States

Unveiling the Coexistence of Cis and Trans Isomers in the Hydrolysis of ZrO2: A Coupled DFT and High-Resolution Photoelectron Spectroscopy Study

∆SCF Dyson Orbitals and Pole Strengths from Natural Ionization Orbitals

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