X-ray absorption and resonant Auger spectroscopy of O(2) in the vicinity of the O 1s ->sigma* resonance: Experiment and theory

X-ray absorption and resonant Auger spectroscopy of O(2) in the vicinity of the O 1s ->sigma* resonance : Experiment and theory

QC 20100916
We report on an experimental and theoretical investigation of x-ray absorption and resonant Auger electron spectra of gas phase O(2) recorded in the vicinity of the O 1s ->sigma* excitation region. Our investigation shows that core excitation takes place in a region with multiple crossings of potential energy curves of the excited states. We find a complete breakdown of the diabatic picture for this part of the x-ray absorption spectrum, which allows us to assign an hitherto unexplained fine structure in this spectral region. The experimental Auger data reveal an extended vibrational progression, for the outermost singly ionized X (2)Pi(g) final state, which exhibits strong changes in spectral shape within a short range of photon energy detuning (0 eV>Omega>-0.7 eV). To explain the experimental resonant Auger electron spectra, we use a mixed adiabatic/diabatic picture selecting crossing points according to the strength of the electronic coupling. Reasonable agreement is found between experiment and theory even though the nonadiabatic couplings are neglected. The resonant Auger electron scattering, which is essentially due to decay from dissociative core-excited states, is accompanied by strong lifetime-vibrational and intermediate electronic state interferences as well as an interference with the direct photoionization channel. The overall agreement between the experimental Auger spectra and the calculated spectra supports the mixed diabatic/adiabatic picture.

NATURVETENSKAP Kemi Teoretisk kemi hsv//swe
NATURAL SCIENCES Chemical Sciences Theoretical Chemistry hsv//eng
NATURVETENSKAP Fysik Atom- och molekylfysik och optik hsv//swe
NATURAL SCIENCES Physical Sciences Atom and Molecular Physics and Optics hsv//eng
NATURVETENSKAP Fysik hsv//swe
NATURAL SCIENCES Physical Sciences hsv//eng
Auger electron spectroscopy
Electron scattering
Electronic states
Excited states
Potential energy
Vibrational spectra
X ray absorption
Resonant Auger spectroscopy
Spectral region
Vicinity
Theoretical chemistry
Teoretisk kemi
Physics
Fysik

Velkov, YasenKTH,Teoretisk kemi(Swepub:kth)u1fun1o4 (author)
Carravetta, V. (author)
Angeli, C. (author)
Cimiraglia, R. (author)
Salek, PawelKTH,Teoretisk kemi(Swepub:kth)u1jnpnxh (author)
Gel'mukhanov, FarisKTH,Teoretisk kemi(Swepub:kth)u1tlrmzw (author)
Sorensen, S. L. (author)
Piancastelli, M. N.Uppsala universitet,Yt- och gränsskiktsvetenskap (author)
De Fanis, A. (author)
Okada, K. (author)
Kitajima, M. (author)
Tanaka, T. (author)
Tanaka, H. (author)
Ueda, K. (author)
Ristinmaa Sörensen, StaceyLund University,Lunds universitet,Synkrotronljusfysik,Fysiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Synchrotron Radiation Research,Department of Physics,Departments at LTH,Faculty of Engineering, LTH(Swepub:lu)slju-sri (author)
Uppsala universitetMjukröntgenfysik (creator_code:org_t)

In:Journal of Chemical Physics: American Institute of Physics (AIP)128:60021-96061089-7690

By the author/editor: Feifel, R.; Velkov, Yasen; Carravetta, V.; Angeli, C.; Cimiraglia, R.; Salek, Pawel; show more...; Gel'mukhanov, Fa ...; Sorensen, S. L.; Piancastelli, M. ...; De Fanis, A.; Okada, K.; Kitajima, M.; Tanaka, T.; Tanaka, H.; Ueda, K.; Ristinmaa Sörens ...; show less...

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Theoretical Chem ...

NATURAL SCIENCES: NATURAL SCIENCES; and Physical Science ...; and Atom and Molecul ...

By the university: Royal Institute of Technology; Lund University; Uppsala University

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