TY - JOUR
T1 - Effects of molecular potential and geometry on atomic core-level photoemission over an extended energy range
T2 - The case study of the CO molecule
AU - Kukk, E.
AU - Ayuso, D.
AU - Thomas, T. D.
AU - Decleva, P.
AU - Patanen, M.
AU - Argenti, L.
AU - Plésiat, E.
AU - Palacios, A.
AU - Kooser, K.
AU - Travnikova, O.
AU - Mondal, S.
AU - Kimura, M.
AU - Sakai, K.
AU - Miron, C.
AU - Martín, F.
AU - Ueda, K.
PY - 2013/9/10
Y1 - 2013/9/10
N2 - We report an experimental and theoretical study of single-molecule inner-shell photoemission measured over an extended range of photon energies. The vibrational intensity ratios I(ν=1)/I(ν=0) from the C 1s photoelectron spectra of carbon monoxide, although mostly determined by the bond length change upon ionization, are shown to be affected also by photoelectron recoil and by scattering from the neighboring oxygen atom. Static-exchange density functional theory (DFT) is used to encompass all these effects in a unified theoretical treatment. The ab initio calculations show that the vibrational ratio as a function of the photoelectron momentum is sensitive to both the ground-state internuclear distance and its contraction upon photoionization. We present a proof-of-principle application of DFT calculations as a quantitative structural analysis tool for extracting the dynamic and static molecular geometry parameters simultaneously.
AB - We report an experimental and theoretical study of single-molecule inner-shell photoemission measured over an extended range of photon energies. The vibrational intensity ratios I(ν=1)/I(ν=0) from the C 1s photoelectron spectra of carbon monoxide, although mostly determined by the bond length change upon ionization, are shown to be affected also by photoelectron recoil and by scattering from the neighboring oxygen atom. Static-exchange density functional theory (DFT) is used to encompass all these effects in a unified theoretical treatment. The ab initio calculations show that the vibrational ratio as a function of the photoelectron momentum is sensitive to both the ground-state internuclear distance and its contraction upon photoionization. We present a proof-of-principle application of DFT calculations as a quantitative structural analysis tool for extracting the dynamic and static molecular geometry parameters simultaneously.
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U2 - 10.1103/PhysRevA.88.033412
DO - 10.1103/PhysRevA.88.033412
M3 - Article
AN - SCOPUS:84884826015
VL - 88
JO - Physical Review A - Atomic, Molecular, and Optical Physics
JF - Physical Review A - Atomic, Molecular, and Optical Physics
SN - 1050-2947
IS - 3
M1 - 033412
ER -