TY - JOUR
T1 - Molecular double core hole electron spectroscopy for chemical analysis
AU - Tashiro, Motomichi
AU - Ehara, Masahiro
AU - Fukuzawa, Hironobu
AU - Ueda, Kiyoshi
AU - Buth, Christian
AU - Kryzhevoi, Nikolai V.
AU - Cederbaum, Lorenz S.
N1 - Funding Information:
M.E. acknowledges the support from JST-CREST and a Grant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science, the Next Generation Supercomputing Project, and the Molecular-Based New Computational Science Program, NINS. H.F. and K.U. acknowledge the support for the X-ray Free Electron Laser Utilization Research Project of Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT). C.B. was supported by National Science Foundation under the Grant Nos. PHY-0701372 and PHY-0449235. The Heidelberg group is grateful for financial support by the Deutsche Forschungsgemeinschaft. The computations were partly performed using the Research Center for Computational Science, Okazaki, Japan.
PY - 2010
Y1 - 2010
N2 - We explore the potential of double core hole electron spectroscopy for chemical analysis in terms of x-ray two-photon photoelectron spectroscopy. The creation of deep single and double core vacancies induces significant reorganization of valence electrons. The corresponding relaxation energies and the interatomic relaxation energies are evaluated by complete active space self-consistent field (CASSCF) calculations. We propose a method on how to experimentally extract these quantities by the measurement of single ionization potentials (IPs) and double core hole ionization potentials (DIPs). The influence of the chemical environment on these DIPs is also discussed for states with two holes at the same atomic site and states with two holes at two different atomic sites. Electron density difference between the ground and double core hole states clearly shows the relaxations accompanying the double core hole ionization. The effect is also compared to the sensitivity of single core hole IPs arising in single core hole electron spectroscopy. We have demonstrated the method for a representative set of small molecules LiF, BeO, BF, CO, N2, C2 H2, C2 H4, C2 H6, COTo avoid confusion, we should note that the definition of ROHF operators J o= m J m and K o = m K m used in Eq. and below slightly differs from that first introduced by Roothaan (Ref.), J o (R) and K o (R): J o = J o (R)/f and Ko = K o (R)/f2, and N 2 O. The scalar relativistic effect on IPs and on DIPs are briefly addressed.
AB - We explore the potential of double core hole electron spectroscopy for chemical analysis in terms of x-ray two-photon photoelectron spectroscopy. The creation of deep single and double core vacancies induces significant reorganization of valence electrons. The corresponding relaxation energies and the interatomic relaxation energies are evaluated by complete active space self-consistent field (CASSCF) calculations. We propose a method on how to experimentally extract these quantities by the measurement of single ionization potentials (IPs) and double core hole ionization potentials (DIPs). The influence of the chemical environment on these DIPs is also discussed for states with two holes at the same atomic site and states with two holes at two different atomic sites. Electron density difference between the ground and double core hole states clearly shows the relaxations accompanying the double core hole ionization. The effect is also compared to the sensitivity of single core hole IPs arising in single core hole electron spectroscopy. We have demonstrated the method for a representative set of small molecules LiF, BeO, BF, CO, N2, C2 H2, C2 H4, C2 H6, COTo avoid confusion, we should note that the definition of ROHF operators J o= m J m and K o = m K m used in Eq. and below slightly differs from that first introduced by Roothaan (Ref.), J o (R) and K o (R): J o = J o (R)/f and Ko = K o (R)/f2, and N 2 O. The scalar relativistic effect on IPs and on DIPs are briefly addressed.
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U2 - 10.1063/1.3408251
DO - 10.1063/1.3408251
M3 - Article
AN - SCOPUS:77952678771
VL - 132
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 18
M1 - 184302
ER -