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Density functional theory calculation of 2p spectra of SiH 4 , PH 3 , H 2 S, HCl, and Ar
Author(s) -
Chong Delano P.,
Segala Maximiliano,
Takahata Yuji,
Baerends E. J.
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21643
Subject(s) - chemistry , spectral line , density functional theory , ionization , atomic physics , electron , valence (chemistry) , absorption spectroscopy , basis set , core electron , valence electron , ionization energy , computational chemistry , physics , quantum mechanics , ion , organic chemistry
The method developed recently for prediction of 1s electron spectra is now extended to the 2p spectra of SiH 4 , PH 3 , H 2 S, HCl, and Ar. The method for X‐ray absorption spectra involves the use of Δ E for the excitation and ionization energies, and application of time‐dependent density functional theory using the exchange‐correlation potential known as statistical average of orbital potentials for the intensities. Additional assumptions and approximations are also made. The best exchange‐correlation functional E xc for the earlier calculation of Δ E in 1s spectra of C to Ne (namely Perdew–Wang 1986 exchange, combined with Perdew–Wang 1991 correlation) is no longer used in this work on 2p spectra of Si to Ar. Instead, recently tested E xc good for 2p core‐electron binding energies (known as OPTX) for exchange and LYP for correlation, plus scalar zeroth‐order regular approximation is adopted here for the Δ E calculations. Our calculated X‐ray absorption spectra are generally in good agreement with experiment. Although the predictions for the higher excitations suffer from basis set difficulties, our procedure should be helpful in the interpretation of absorption spectra of 2p electrons of Si to Ar. In addition, we report calculated results for other kinds of electron spectra for SiH 4 , PH 3 , H 2 S, HCl, and Ar, including valence electron ionizations and excitations as well as X‐ray emission. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008