Hy, I'm trying to simulate X-Ray photoelectron spectra with Gaussian09. Is it correct that the relaxation energy is just the difference between the HF-SCF-Energies from the (N-1) electron wavefunction of an DFT geometry optimized N electron wavefunction, so that the ionization energies can be calculated by addition of this relaxation energy to the KS-Orbitals from optimization of the N electron wavefuntion?
From the following publication (S. 6-8) I understand this the approximation for the final state effects:
Paul S. Bagus, Eugene S. Ilton, Connie J. Nelin, The interpretation of XPS spectra: Insights into materials properties, Surface Science Reports, Volume 68, Issue 2, 1 June 2013, Pages 273-304
What about the sudden approximation? How to calculate the unrelaxed wavefunction with the k-hole at time t=0 to separate the initial from final state effects? I tried to use guess=alter in a UHF single point calculation to transpose a core orbital to the highest virtual orbitals but I get the same SCF-Energies by variation for different core hole orbitals? Do I have to use tddft instead to calculate the core hole wavefunctions? I hope someone here understand my problems, otherwise please ask, If my question was unclear.
Best regards
Sebastian
Links
http://www.rug.nl/research/portal/files/6774494/2012ChemPhysKlooster.pdf
http://pubs.acs.org/doi/abs/10.1021/ar50030a003?journalCode=achre4
http://www.diss.fu-berlin.de/diss/servlets/MCRFileNodeServlet/FUDISS_derivate_000000001803/04_chapter4.pdf;hosts=
http://www2.cemr.wvu.edu/~wu/mae649/xps.pdf
Thank you very much, William! I will check the links immediateley.
https://books.google.co.in/books?id=QbDEC3oL7uAC&pg=PA359&lpg=PA359&dq=How+to+perform+Frozen+Orbital+Approximation+to+calculate+relative+Intensities+in+XPS&source=bl&ots=S5mlnL9rxG&sig=IJnXSE0dGyBwVmY8dz9DmT9Emr4&hl=en&sa=X&ved=0ahUKEwju1p20jJDTAhUIsY8KHYDiAucQ6AEIJzAD#v=onepage&q=How%20to%20perform%20Frozen%20Orbital%20Approximation%20to%20calculate%20relative%20Intensities%20in%20XPS&f=false
https://web.statler.wvu.edu/~wu/mae649/xps.pdf
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