Problem with Co 2p XPS simulation

Dear Sayari,

I would suggest to start with the example you find here https://git.quanty.org:4443/Haverkort/tutorials/-/tree/main/08_Materials/NiO/02%20NiO%20Ligand%20field%20theory/17%20cPES%20L23?ref_type=heads and modify it to get the 2p XPS for Co.

You will need to modify the following set of parameters

 
-- number of electrons (formal valence)
nd = 8                    --> 6
-- parameters from experiment (core level PES)
Udd     =  7.3
Upd     =  8.5
Delta   =  4.7
-- parameters obtained from DFT (PRB 85, 165113 (2012))
F2dd    = 11.14 
F4dd    =  6.87
F2pd    =  6.67
G1pd    =  4.92
G3pd    =  2.80
tenDq   =  0.56
tenDqL  =  1.44
Veg     =  2.06
Vt2g    =  1.21
zeta_3d =  0.081
zeta_2p = 11.51
Bz      =  0.000001
Hz      =  0.120           --> 0

for the other parameters see Phys. Rev. Lett. 97, 176405. The Hartree Fock values of the Slater integrals you can find on page 156 of https://kups.ub.uni-koeln.de/1455/ or https://arxiv.org/abs/cond-mat/0505214.

If you want to understand how this example works you can also look at the examples found here https://git.quanty.org:4443/Haverkort/tutorials/-/tree/main/08_Materials/NiO/02%20NiO%20Ligand%20field%20theory?ref_type=heads

best wishes, Maurits

Dear Sayari,

you can find the documentation of the operators

Coulomb repulsion operator (U)

Crystal Field

Maurits

Dear Sir,

First of all, I would like to sincerely thank you for your prompt response and guidance. I also apologize for my delayed reply. External LinkExternal Link Over the past few weeks, I have gone through the Quanty documentation carefully and tried to understand the basics of its implementation. As an initial step, I reproduced the NiO example successfully, which gave me confidence to proceed.

After that, I moved on to Co 2p XPS simulations for LaCoO₃ in different spin states. Alongside the PRL paper you kindly suggested, I referred to two other works for c parameters and guidance: Vankó et al., Phys. Rev. B 73, 024424 (2006) ,Takegami et al., Phys. Rev. X 13, 011037 (2023).

My initial aim was to simulate the high-spin (HS) Co³⁺ spectrum so that I could compare it with my experimental 623 K Co 2p data and tune the parameters accordingly. Once optimized, I planned to vary 10Dq (and possibly Δ) to simulate the intermediate-spin (IS) and low-spin (LS) spectra, to systematically compare them with experiment.

So far, I have attempted three different trials:

Trial 1: Used Slater integrals (F, G) and SOC values directly from the NiO example, and other parameters from your suggested paper.

Trial 2 & 3: Used 90% of Hartree–Fock values for Slater integrals and atomic values for SOC, as in https://kups.ub.uni-koeln.de/1455/.

However, I remain stuck at the HS simulation stage. In each case, the main challenge is that the simulated spectra do not reproduce the experimental separation between multiplet structures and satellite s (~10 eV from the main line). To address this, I tried systematically increasing zeta_p, Veg, and Δ. Unfortunately, the splitting and multiplet features remain very weak in the simulations.

In my experimental Co 2p spectra, there is also an emergent feature at ~786 eV with increasing temperature, which is often considered a hallmark of the spin-state transition. My simulated HS spectra, however, do not capture this behavior.

I have been using the isotropic average transition operator (no polarization), consistent with my laboratory setup where the detector is placed at 90°.The charge-transfer multiplet (CTM) model employed a ground-state basis set of 3𝑑6+3𝑑7𝐿‾+3𝑑8𝐿‾23d6.

To give you a clearer picture, I am attaching:One of my Quanty scripts from a trial, Three slides summarizing parameter sets used in different attempts. I would be truly grateful for your advice on which parameter set or modeling adjustment I should focus on to correctly reproduce the spin–orbit splitting and satellite features in the HS spectrum.

Thank you again for your time and guidance.

With best regards, Sayari Ghatak