Predicting core electron binding energies in elements of the first transition series using the...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Spectroscopy

Background:

• The Delta-Self-Consistent-Field (ΔSCF) method is established for light elements.
• Its performance for heavier elements, particularly transition metals, is less understood.

Purpose of the Study:

• To evaluate the accuracy of ΔSCF for transition metal 2p core electron binding energies.
• To assess the influence of chemical environment on ΔSCF accuracy for these elements.

Main Methods:

• Performed ΔSCF calculations on 60 molecular compounds of first-row transition metals (Ti, V, Cr, Mn, Fe, Co).
• Compared calculated binding energies with experimental gas-phase photoelectron spectroscopy data.

Main Results:

• Calculated TM 2p binding energies showed a mean absolute error (MAE) of 0.73 eV compared to experimental data.
• The error was found to be element-dependent and largely insensitive to the chemical environment.
• An element-specific correction reduced the MAE to 0.20 eV, enhancing accuracy.

Conclusions:

• ΔSCF is a viable method for transition metal core binding energies with element-specific corrections.
• The findings provide a more accurate computational approach for studying these systems.