Communication: Stabilization of radical anions with weakly bound electron in condensed media: A case study of diacetonyl radical anion

Saenko, Elizaveta V.; Laikov, Dimitri N.; Баранова, И. А.; Feldman, Vladimir I.

doi:10.1063/1.3638690

Cited by 14 publications

(3 citation statements)

References 22 publications

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“…While the HCOOH molecule has no intrinsic electron affinity, 69 most probably, it cannot scavenge thermalized excess electrons in non-polar, low polarizable matrices, as it was shown for some other carbonyl compounds. 70 Indeed, there is no evidence for stabilization of the HCOOH À radical anion in any noble gas matrix studied in this work. On the other hand, in general, one cannot exclude dissociative electron attachment (DEA) due to the reaction of formic acid molecules with low-energy non-thermal secondary electrons.…”

Section: Discussionmentioning

confidence: 66%

Radiation-induced transformations of matrix-isolated formic acid: evidence for the HCOOH → HOCO + H channel

Ryazantsev

Feldman

2015

Phys. Chem. Chem. Phys.

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The effect of X-ray irradiation on the isolated formic acid molecules (HCOOH) in solid noble gas matrices (Xe, Kr, Ar, and Ne) at very low temperatures (6 K) was first studied by FTIR spectroscopy. Carbon oxides (CO and CO2) and hydrocarboxyl radicals (HOCO) have been detected as the principal degradation products. The formation of HOCO radicals represents a primary dissociation channel for formic acid, which was not reported previously under UV photolysis in solids. This reaction can be explained by the involvement of the recombination-induced excited states, which are not populated in photolysis. The effects of the matrix and the absorbed dose on the product formation were studied in detail and possible mechanisms are discussed with particular attention to the difference between radiolysis and UV-photolysis of the matrix-isolated formic acid. The results obtained provide a new insight into the effects of high-energy impact on the simplest carboxylic acid with possible implications to the astrochemical problems, in particular, the prebiotic evolution in the interstellar medium.

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Section: Discussionmentioning

confidence: 66%

Radiation-induced transformations of matrix-isolated formic acid: evidence for the HCOOH → HOCO + H channel

Ryazantsev

Feldman

2015

Phys. Chem. Chem. Phys.

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“…We sought a general solution to this problem. Lowest Rydberg states were tried in this role 85 , but are too diffuse for a typical use. From the known connection between the ionization potential and the long-range behavior 86,87 of the density follows that a minimal set of diffuse functions (one for each angular symmetry) cannot fit for all imaginable an-ionic (or even neutral) species, and a lower bound for the ionization potential should be set anyway.…”

Section: Introductionmentioning

confidence: 99%

Atomic basis functions for molecular electronic structure calculations

Laikov

2019

Theor Chem Acc

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Electronic structure methods for accurate calculation of molecular properties have a high cost that grows steeply with the problem size, therefore, it is helpful to have the underlying atomic basis functions that are less in number but of higher quality. Following our earlier work [Chem. Phys. Lett. 416, 116 (2005)] where general correlation-consistent basis sets are defined, for any atom, as solutions of purely atomic functional minimization problems, and which are shown to work well for chemical bonding in molecules, we take a further step here and define a new kind of atomic polarization functionals, the minimization of which yields additional sets of diffuse functions that help to calculate better molecular electron affinities, polarizabilities, and intermolecular dispersion interactions. Analytical representations by generally-contracted Gaussian functions of up to microhartree numerical accuracy grades are developed for atoms Hydrogen through Nobelium within the four-component Dirac-Coulomb theory and its scalar-relativistic approximation, and also for Hydrogen through Krypton in the two-component nonrelativistic case. The convergence of correlation energy with the basis set size is studied, and complete-basis-set extrapolation formulas are developed.

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“…Most of the experimental data on anion resonances come from electron energy loss spectroscopy (EELS) and electron transmission spectroscopy (ETS) whose typical resolution (>30 meV) − is often insufficient to obtain line widths representative of the autodetachment lifetime. For species with a stable ground-state anion, matrix absorption experiments − can also be used to probe optically allowed anion electronic transitions, but the presence of the matrix can strongly distort the autodetachment lifetime.…”

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confidence: 99%

Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances

Sagan

Anstöter

Thodika

et al. 2022

J. Phys. Chem. Lett.

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The positions and widths of the optically allowed electronic states of the tetracene radical anion located above the detachment threshold energy (i.e anion resonances) are mapped out using total photodetachment yield spectroscopy of cryogenically cooled ions. The presence of these states is detected via the sharp increase in the photodetachment yield compared to that of the monotonic nonresonant direct photodetachment background. The resolution of the resulting spectrum is limited by the ∼5 cm–1 line width of the tunable laser and thus provides a stringent benchmark for computations of the energies and autodetachment lifetimes of these resonance states. The experimental results are compared to high-level electronic structure computations and line width modeling using the orbital stabilization method. These theoretical results are found to be in near quantitative agreement with the experimental data, highlighting their capability to accurately describe the energies and lifetimes of anion resonances for relatively large molecules.

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Communication: Stabilization of radical anions with weakly bound electron in condensed media: A case study of diacetonyl radical anion

Cited by 14 publications

References 22 publications

Radiation-induced transformations of matrix-isolated formic acid: evidence for the HCOOH → HOCO + H channel

Radiation-induced transformations of matrix-isolated formic acid: evidence for the HCOOH → HOCO + H channel

Atomic basis functions for molecular electronic structure calculations

Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances

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