Autoionization widths by Stieltjes imaging applied to Lanczos pseudospectra

Journal Article · Fri Jan 14 00:00:00 EST 2011 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3523982· OSTI ID:21559971

Kopelke, S; Gokhberg, K; Cederbaum, L S ^[1]; Tarantelli, F ^[2]; Averbukh, V ^[3]

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1. Theoretische Chemie, Physikalisch-Chemisches Institut, Universitaet Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)
2. Dipartimento di Chimica, Universita degli Studi di Perugia and CNR I.S.T.M., Via Elce di Sotto 8, 06123 Perugia (Italy)
3. Department of Physics, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom)

Excited states of atoms and molecules lying above the ionization threshold can decay by electron emission in a process commonly known as autoionization. The autoionization widths can be calculated conveniently using Fano formalism and discretized atomic and molecular spectra by a standard procedure referred to as Stieltjes imaging. The Stieltjes imaging procedure requires the use of the full discretized spectrum of the final states of the autoionization, making its use for poly-atomic systems described by high-quality basis sets impractical. Following our previous work on photoionization cross-sections, here we show that also in the case of autoionization widths, the full diagonalization bottleneck can be overcome by the use of Lanczos pseudospectra. We test the proposed method by calculating the well-documented autoionization widths of inner-valence-excited neon and apply the new technique to autoionizing states of hydrofluoric acid and benzene.

• OSTI ID: 21559971
• Journal Information: Journal of Chemical Physics, Vol. 134, Issue 2; Other Information: DOI: 10.1063/1.3523982; (c) 2011 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ATOMS
AUTOIONIZATION
BENZENE
CROSS SECTIONS
ELECTRON EMISSION
EXCITED STATES
HYDROFLUORIC ACID
MOLECULES
NEON
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
PHOTON-ATOM COLLISIONS
PHOTON-MOLECULE COLLISIONS
SPECTRA
WIDTH
AROMATICS
ATOM COLLISIONS
COLLISIONS
DIMENSIONS
ELECTRON SPECTROSCOPY
ELEMENTS
EMISSION
ENERGY LEVELS
FLUIDS
FLUORINE COMPOUNDS
GASES
HALOGEN COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
INORGANIC COMPOUNDS
IONIZATION
MOLECULE COLLISIONS
NONMETALS
ORGANIC COMPOUNDS
PHOTON COLLISIONS
RARE GASES
SPECTROSCOPY