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Influence of chemical bonds on the lifetime of the molecular-field-split 2p levels in H2S

Bueno, AM; de Brito, AN; Fink, RF; Bassler, M; Bjorneholm, O; Burmeister, F; Feifel, R; Miron, C; Ristinmaa Sörensen, Stacey LU and Wang, HH, et al. (2003) In Physical Review A (Atomic, Molecular and Optical Physics) 67(2).
Abstract
Different lifetime broadenings in molecular-field-split 2p core levels in H2S are predicted theoretically and are identified in an experimental investigation of the S 2p Auger electron spectrum. The measurements were performed for the transition to the vibrationally resolved X(1)A(1) ground state of H2S2+. The lifetimes of the 3e(1/2) and 5e(1/2) levels of the 2p ionized molecule are found to be 64 and 74 meV, respectively. This unambiguous determination of the lifetime difference of 10+/-1 meV is only possible as the 4e(1/2)-->X(1)A(1)(2b(1)(-2)) decay channel that overlaps the 5e(1/2)-->X(1)A(1)(2b(1)(-2)) channel is practically suppressed in Auger decay in H2S. The lifetime difference is confirmed by ab initio calculations. A... (More)
Different lifetime broadenings in molecular-field-split 2p core levels in H2S are predicted theoretically and are identified in an experimental investigation of the S 2p Auger electron spectrum. The measurements were performed for the transition to the vibrationally resolved X(1)A(1) ground state of H2S2+. The lifetimes of the 3e(1/2) and 5e(1/2) levels of the 2p ionized molecule are found to be 64 and 74 meV, respectively. This unambiguous determination of the lifetime difference of 10+/-1 meV is only possible as the 4e(1/2)-->X(1)A(1)(2b(1)(-2)) decay channel that overlaps the 5e(1/2)-->X(1)A(1)(2b(1)(-2)) channel is practically suppressed in Auger decay in H2S. The lifetime difference is confirmed by ab initio calculations. A theoretical analysis shows that it results from the mutual orientation of the core hole in the intermediate states and the valence electron density in the sulfur 3p orbitals. Both are strongly influenced by the chemical bond. Thus the observed effect is the direct result of a fundamental property of molecular electronic structure. (Less)
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Physical Review A (Atomic, Molecular and Optical Physics)
volume
67
issue
2
publisher
American Physical Society
external identifiers
  • wos:000181361200071
  • scopus:0038301321
ISSN
1050-2947
DOI
10.1103/PhysRevA.67.022714
language
English
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yes
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4a715d6f-73fa-416a-841e-18af25e01763 (old id 908848)
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2008-01-10 18:26:58
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2018-09-09 03:30:58
@article{4a715d6f-73fa-416a-841e-18af25e01763,
  abstract     = {Different lifetime broadenings in molecular-field-split 2p core levels in H2S are predicted theoretically and are identified in an experimental investigation of the S 2p Auger electron spectrum. The measurements were performed for the transition to the vibrationally resolved X(1)A(1) ground state of H2S2+. The lifetimes of the 3e(1/2) and 5e(1/2) levels of the 2p ionized molecule are found to be 64 and 74 meV, respectively. This unambiguous determination of the lifetime difference of 10+/-1 meV is only possible as the 4e(1/2)-->X(1)A(1)(2b(1)(-2)) decay channel that overlaps the 5e(1/2)-->X(1)A(1)(2b(1)(-2)) channel is practically suppressed in Auger decay in H2S. The lifetime difference is confirmed by ab initio calculations. A theoretical analysis shows that it results from the mutual orientation of the core hole in the intermediate states and the valence electron density in the sulfur 3p orbitals. Both are strongly influenced by the chemical bond. Thus the observed effect is the direct result of a fundamental property of molecular electronic structure.},
  articleno    = {022714},
  author       = {Bueno, AM and de Brito, AN and Fink, RF and Bassler, M and Bjorneholm, O and Burmeister, F and Feifel, R and Miron, C and Ristinmaa Sörensen, Stacey and Wang, HH and Svensson, S},
  issn         = {1050-2947},
  language     = {eng},
  number       = {2},
  publisher    = {American Physical Society},
  series       = {Physical Review A (Atomic, Molecular and Optical Physics)},
  title        = {Influence of chemical bonds on the lifetime of the molecular-field-split 2p levels in H2S},
  url          = {http://dx.doi.org/10.1103/PhysRevA.67.022714},
  volume       = {67},
  year         = {2003},
}