Autoionization widths by Stieltjes imaging applied to Lanczos pseudospectra

Journal Article · Fri Jan 14 04:00:00 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, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 134; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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