Nonvalence states of neutral molecules (Rydberg states) play important roles in nonadiabatic dynamics of excited states. In anions, such nonadiabatic transitions between nonvalence and valence states have been much less explored even though they are believed to play important roles in electron capture and excited state dynamics of anions. The aim of this Feature Article is to provide an overview of recent experimental observations, based on time-resolved photoelectron imaging, of valence to nonvalence and nonvalence to valence transitions in anions and to demonstrate that such dynamics may be commonplace in the excited state dynamics of molecular anions and cluster anions.
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http://dx.doi.org/10.1021/acs.jpca.0c01260 | DOI Listing |
J Phys Chem A
September 2024
Department of Chemistry and Physics, Southeastern Louisiana University, SLU 10878, Hammond, Louisiana 70402, United States.
Anions formed by the perhalobenzene series CClF ( = 0-6) are studied computationally. All members of the series form both stable valence and stable nonvalence anions. At the geometry of the neutral parents, only nonvalence anions are bound, and the respective vertical electron affinities show values in the 20 to 60 meV range.
View Article and Find Full Text PDFJ Phys Chem Lett
August 2024
Department of Chemistry, KAIST, Daejeon 34141, Republic of Korea.
State-specific dynamics of the dipole-bound state (DBS) of the cryogenically cooled deprotonated 4,4'-biphenol anion have been investigated by picosecond time-resolved pump-probe spectroscopy. For DBS vibrational states below the electron-detachment threshold, the relaxation rate is slow to give a lifetime (τ) longer than ∼5 ns, and it is attributed to the nonvalence-to-valence orbital transformation. For the DBS resonances above the detachment threshold, however, the lifetime decreases with the activation of autodetachment, whereas the otherwise zeroth DBS modes seem to be randomized by intramolecular vibrational energy redistribution (IVR), as manifested in the biexponential transients.
View Article and Find Full Text PDFJ Phys Chem Lett
June 2024
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260, United States.
The ground and excited state nonvalence correlation-bound (NVCB) anion states of the hexagonal polycylic aromatic hydrocarbons and of hexagonal graphene nanoflakes are characterized using a one-electron model Hamiltonian which incorporates atomic electrostatic moments up to the quadrupole, coupled inducible charges and dipoles, and atom-centered Gaussians to describe the short-range repulsive interactions. Extrapolation of the calculated electron binding energies of the lowest energy symmetric and antisymmetric (with respect to the molecular plane) NVCB anions of both the polycylic aromatic hydrocarbons and the carbon nanoflakes to the → ∞ limit yields binding energies that are in good agreement with those of the most stable symmetric and antisymmetric image potential states of freestanding graphene as determined from two-photon photoemission spectroscopy (2PPE) experiments.
View Article and Find Full Text PDFAnnu Rev Phys Chem
June 2024
Department of Chemistry, Durham University, Durham, United Kingdom; email:
Gas-phase anions present an ideal playground for the exploration of excited-state dynamics. They offer control in terms of the mass, extent of solvation, internal temperature, and conformation. The application of a range of ion sources has opened the field to a vast array of anionic systems whose dynamics are important in areas ranging from biology to star formation.
View Article and Find Full Text PDFJ Phys Chem Lett
February 2024
Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400005, India.
We propose a single-parameter effective one-particle potential, termed the single-pole exchange-correlation (1p-XC), to rapidly evaluate electron affinities (EAs) of nonvalence electronic states of molecular clusters and nanoassemblies. The model combines exact-exchange and the random phase approximation (RPA) correlation potential with a single-pole approximation to model the frequency-dependent polarization function. It captures long-range static and dynamic-frequency effects in the correlation potential, with mean absolute errors of 0.
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