Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity

Kruppa, Sebastian V.; Groß, Cedric; Gui, Xin; Bäppler, Florian; Kwasigroch, Björn; Sun, Yu; Diller, Rolf; Klopper, Wim; Niedner‐Schatteburg, Gereon; Riehn, Christoph; Thiel, Werner R.

doi:10.1002/chem.201901981

Cited by 7 publications

(5 citation statements)

References 128 publications

(130 reference statements)

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“…Action spectroscopy approaches have yielded key insights in analytical biophysics, , coordination chemistry, − astrophysics, and metal cluster physics . Applications of these methods to metal clusters composed of silver, − copper, gold, − or alloys thereof have successfully elucidated the electronic and geometric structure of ligand-free and ligand-capped clusters using either electron photodetachment or photochemical fragmentation action spectroscopy. The former is suitable for anionic or neutral compounds and exclusively reports on projection into a photoionized potential energy surface, ,,− while spectra acquired by the latter subtly vary upon the photofragmentation mechanism employed.…”

Section: Introductionmentioning

confidence: 99%

High Precision Electronic Spectroscopy of Ligand-Protected Gold Nanoclusters: Effects of Composition, Environment, and Ligand Chemistry

2020

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Atomically precise gold nanoclusters (AuNCs) are a class of nanomaterials valued for their electronic properties and diverse structural features. While the advent of X-ray crystallography of AuNCs has revealed their geometric structures with high precision, detailed electronic structure analysis is challenged by environmental, compositional, and thermal averaging effects present in electronic spectra of typical samples. To circumvent these challenges, we have adapted mass spectrometer-based electronic absorption spectroscopy techniques to acquire high-resolution electronic spectra of atomically precisely defined nanoclusters separated from a synthetic mixture.Here we discuss recent results using this approach to link the surface chemistry of triphenylphosphine-protected AuNCs to their electronic structure and expand on key elements of the experiment and the link between these gas-phase measurements and solution-phase behavior of AuNCs. Chemically derivatized Au 8 (P(p-X-Ph) 3 ) 7 2+ and Au 9 (P(p-X-Ph) 3 ) 8 3+ clusters, where X = −H, −CH 3 , or −OCH 3 , are used to derive systematic trends in the response of the electronic spectrum to the electron-donating character of the ligand shell. We find a linear relationship between the substituent Hammett parameter σ p and the transition energy between both sets of clusters' highest occupied and lowest unoccupied molecular orbitals, a transition that is localized in the metal core within the limits of the superatomic model. The similarity of the mass-selective and solution-phase UV/vis spectra of Au 9 (PPh 3 ) 8 3+ indicates that the interpretation of these experiments is transferable to the condensed phase. He and N 2 environments are introduced to a series of isovalent clusters as a subtle probe of discrete environmental effects over electronic structure. Strikingly, select bands in the UV/vis spectrum respond strongly to the identity of the environment, which we interpret as a state-selective indicator of interfacially relevant electronic transitions. Physically predictable trends such as these will aid in building molecular design principles necessary for the development of novel materials based on nanoclusters.

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Section: Introductionmentioning

confidence: 99%

High Precision Electronic Spectroscopy of Ligand-Protected Gold Nanoclusters: Effects of Composition, Environment, and Ligand Chemistry

2020

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“…136,137 To illustrate the applicability to systems with heavy elements a model for the Ag 3 H hydrogen transfer complex of Ref. 138, denoted as L-Ag 3 H, and Os(CO) 10 H 2 139 are included in the set. For these molecules, the scalar-relativistic DLU-X2C approach is applied, while calculations for all other molecules use the non-relativistic framework.…”

Section: Methodsmentioning

confidence: 99%

Beyond Electrons: Correlation and Self-Energy in Multicomponent Density Functional Theory

Holzer,

Franzke

2024

Preprint

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Post-Kohn-Sham methods are used to evaluate the ground-state correlation energy and the orbital self-energy of systems consisting of multiple flavors of different fermions. Starting from multicomponent density functional theory, suitable ways to arrive at the corresponding multicomponent random-phase approximation and the multicomponent Green's function GW approximation, including relativistic effects, are outlined. Given the importance of both of this methods in the development of modern Kohn-Sham density functional approximations, this work will provide a foundation to design advanced multicomponent density functional approximations. Additionally, the GW quasiparticle energies are needed to study light-matter interactions with the Bethe-Salpeter equation.

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“…[137,138] To illustrate the applicability to systems with heavy elements a model for the Ag 3 H hydrogen transfer complex of Ref. [139], denoted as L-Ag 3 H, and Os(CO) 10 H 2 [140] are included in the set. For these molecules, the scalar-relativistic DLUÀ X2C approach is applied, while calculations for all other molecules use the non-relativistic framework.…”

Section: Methodsmentioning

confidence: 99%

Beyond Electrons: Correlation and Self‐Energy in Multicomponent Density Functional Theory

Holzer,

Franzke

2024

ChemPhysChem

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Post‐Kohn‐‐Sham methods are used to evaluate the ground‐state correlation energy and the orbital self‐energy of systems consisting of multiple flavors of different fermions. Starting from multicomponent density functional theory, suitable ways to arrive at the corresponding multicomponent random‐phase approximation and the multicomponent Green's function GW approximation, including relativistic effects, are outlined. Given the importance of both of this methods in the development of modern Kohn‐‐Sham density functional approximations, this work will provide a foundation to design advanced multicomponent density functional approximations. Additionally, the GW quasiparticle energies are needed to study light‐matter interactions with the Bethe‐‐Salpeter equation.

show abstract

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity

Cited by 7 publications

References 128 publications

High Precision Electronic Spectroscopy of Ligand-Protected Gold Nanoclusters: Effects of Composition, Environment, and Ligand Chemistry

High Precision Electronic Spectroscopy of Ligand-Protected Gold Nanoclusters: Effects of Composition, Environment, and Ligand Chemistry

Beyond Electrons: Correlation and Self-Energy in Multicomponent Density Functional Theory

Beyond Electrons: Correlation and Self‐Energy in Multicomponent Density Functional Theory

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