DFT calculation of core-electron binding energies

Takahata, Yuji; Chong, Delano P.

doi:10.1016/j.elspec.2003.08.001

Cited by 113 publications

(135 citation statements)

References 56 publications

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“…The ∆E KS (PW86-PW91)/ TZP method works very well. 41 AAD of 0.15 eV had also been obtained previously for exactly the same set of molecules using the uGTS model. 42 The DeMon DFT program was employed in the uGTS calculations.…”

Section: Resultssupporting

confidence: 55%

Is HAM/3 (hydrogenic atoms in molecules, version 3) a semiempirical version of dft (density functional theory) for ionization processes?

Takahata¹,

Chong²

2004

J. Braz. Chem. Soc.

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Nós calculamos os potenciais de ionização verticais (VIPs) de nove moléculas pequenas, bem como, os potenciais de uracil e do C 2 F 2 usando diferentes métodos: i) semi-empírico HAM/3; ii) semi-empírico AM1; iii) não empírico Teoria do Funcional de Densidade (TFD) com os modelos uDI(B88-P86)/cc-pVTZ e -ε(SAOP)/TZP; iv) ab initio HF/cc-pVTZ. Os resultados numéricos obtidos com HAM/3 são mais próximos dos resultados obtidos com o TFD do que o Hartree-Fock (HF). Nós também calculamos as energias de ligação de elétrons do caroço (CEBE) da anilina, nitrobenzeno, e p-nitroanilina com o HAM/3 e a TFD empregando o método ∆E. O modelo de DFT designado como ∆E KS (PW86-PW91)/TZP produziu resultados precisos de CEBE, com desvio médio absolutos de 0,14 eV. Enquanto que a magnitude absoluta dos CEBEs calculados pelo método HAM/3 tem um erro de menos de 3 eV, os deslocamentos químicos (∆CEBE) têm erros menores que 0,55 eV. Mesmo que os resultados de CEBE não apresentem uma resposta definitiva à pergunta do título, as tendências nos VIPs indicam que o HAM/3 não se aproxima do TFD com potenciais de troca-correlação precisos, mas indicam uma proximidade com funcionais semelhantes ao B88-P86.We calculated valence-electron vertical ionization potentials (VIPs) of nine small molecules, plus uracil and C 2 F 4 , by several different methods: semiempirical HAM/3 and AM1 methods, different nonempirical DFT models such as uDI(B88-P86)/cc-pVTZ and -ε(SAOP)/TZP, and ab initio Hartree-Fock (HF) /cc-pVTZ. HAM/3 reproduced numerical values more closely to those calculated by the nonempirical DFTs than to those obtained by HF method. Core-electron binding energies (CEBEs) of aniline, nitrobenzene and p-nitro aniline, were also calculated by HAM/3 and nonempirical ∆FT using DE method. A nonempirical DFT model, designated as ∆E KS (PW86-PW91)/TZP model, resulted accurate CEBEs (average absolute deviation of 0.14 eV) with high efficiency. Although absolute magnitude of HAM/3 CEBEs has error as much as 3 eV, the error in the chemical shifts ∆CEBE is much smaller at 0.55 eV. While the CEBE results do not lead to any definite answer to the question in the title, the trends in valence-electron VIPs indicate that HAM/3 does not approximate DFT with accurate exchange-correlation potentials, but seems to simulate approximate functionals such as B88-P86.Keywords: HAM/3, DFT, vertical ionization potential, CEBE, ESCA IntroductionThe semiempirical molecular orbital (MO) method known as Hydrogenic Atoms in Molecules, Version 3 (HAM/3) was developed by group of Lindholm and coworkers in 1977. 1 The method has been successfully applied to the calculation of mainly vertical ionization potentials (VIPs), excitation energies, and electron affinities of wide variety of molecules. Some selected works are listed in references 2-7. However, extensions of HAM/3 to the calculation of X-ray emission spectra, 8 Auger electron spectra, 9 valence-electron shake-up satellites, 10 core-electron shake-up satellites, 11 and relative intensities for valence region of X-ray p...

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Section: Resultssupporting

confidence: 55%

Is HAM/3 (hydrogenic atoms in molecules, version 3) a semiempirical version of dft (density functional theory) for ionization processes?

Takahata¹,

Chong²

2004

J. Braz. Chem. Soc.

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“…In another study using a SCF approach, it was found that CEBEs calculated with large basis sets could be reproduced to within 0.2 eV by optimising the exponents and contraction coefficients of relatively small basis sets for the core-hole state [47]. The use of Slater-type basis functions has also been explored for the calculation of CEBEs and the results indicate that polarised triple-zeta basis set of Slater-type orbitals to be adequate [48]. In more recent work, the performance of a range of basis sets and exchange-correlation functionals was investigated for the calculation of CEBEs of first-row hydrides and glycine [50].…”

Section: Introductionmentioning

confidence: 99%

“…The description of the cusp at the nuclei is a well-known deficiency of Gaussian basis sets. Basis sets of Slater-type orbitals will describe the cusp behaviour more accurately, and some preliminary studies using basis sets of Slater-type orbitals have been reported in the literature [48]. Table 8 shows MAD (pcSseg-4) for the core → LUMO transition energies computed using TDDFT.…”

Section: Scf Core-electron Binding Energies and Core-excitation Energiesmentioning

confidence: 99%

“…Several studies have considered the basis set dependence of CEBEs calculations using a SCF approach in conjunction with density functional theory (DFT) or Møller-Plesset perturbation theory [9,[45][46][47][48][49][50]. It has been reported that the core-valence correlated triple-zeta basis set (cc-pCVTZ) to be accurate and efficient compared with the cc-pV5Z basis set.…”

Section: Introductionmentioning

confidence: 99%

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Assessment of basis sets for density functional theory-based calculations of core-electron spectroscopies

Fouda

Besley

2017

Theor Chem Acc

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The performance of Gaussian basis sets for density functional theory-based calculations of core-electron spectroscopies is assessed. The convergence of core-electron binding energies and core-excitation energies using a range of basis sets including split-valence, correlation-consistent, polarisation-consistent and individual gauge for localised orbitals basis sets is studied. For self-consistent field calculations of core-electron binding energies and core-excitation energies of first-row elements, relatively small basis sets can accurately reproduce the values of much larger basis sets, with the IGLO basis sets performing particularly well. Calculations for the K-edge of second-row elements are more challenging, and of the smaller basis sets, pcSseg-2 has the best performance. For the correlation-consistent basis sets, inclusion of core-valence correlation functions is important, with the cc-pCVTZ basis set giving accurate results. Time-dependent density functional theory-based calculations of core-excitation energies show less sensitivity to the basis set with relatively small basis sets, such as pcSseg-1 or pcSseg-2, reproducing the values for much larger basis sets accurately. In contrast, time-dependent density functional theory calculations of X-ray emission energies are highly dependent on the basis set, but the IGLO-II, IGLO-III and pcSseg-2 basis sets provide a good level of accuracy.

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“…This method for CEBEs of organic and other small molecules have been tested on many systems. [21,22] For excitation of valence electrons, the procedure of time-dependent density functional theory (TDDFT) using Vxc = SAOP has been tested in many molecules. The TDDFT procedure produces excited singlet states with oscillator strengths as well as triplet states.…”

Section: Computation Detailsmentioning

confidence: 99%

Computational Study of the Electron Spectra of Acetamide and N-methylformamide

Chong¹

2017

Croat. Chem. Acta

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Abstract:The molecular structures of the three conformers of acetamide are first studied by ab initio method of CCSD/cc-pVTZ. Using the optimized geometry of each species, we apply established and/or developing methods to compute several physical properties of acetamide and compare them with available experimental data. The properties include dipole moments, polarizabilities, ionization energies of both valence and core electrons, and absorption spectra of both valence and core electrons. Similar results for N-methylformamide are included for comparison.

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DFT calculation of core-electron binding energies

Cited by 113 publications

References 56 publications

Is HAM/3 (hydrogenic atoms in molecules, version 3) a semiempirical version of dft (density functional theory) for ionization processes?

Is HAM/3 (hydrogenic atoms in molecules, version 3) a semiempirical version of dft (density functional theory) for ionization processes?

Assessment of basis sets for density functional theory-based calculations of core-electron spectroscopies

Computational Study of the Electron Spectra of Acetamide and N-methylformamide

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