Prediction of core electron binding energies with a four-parameter equation

Jolly, William L.; Bakke, Albert A.

doi:10.1021/ja00437a013

Cited by 26 publications

(8 citation statements)

References 3 publications

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“…Older, low-resolution measurements give only the vertical energy. Also included here are the results of other measurements for 15 other halomethanes. ,− For the data from the literature some modifications have been made to the reported results, reflecting changes in the values of reference energies. For instance, the ionization energies given by Perry and Jolly 16 are, on the average, 0.13 eV lower than the most recent values.…”

Section: Experimental Procedures and Experimental Resultsmentioning

confidence: 99%

Carbon 1s Photoelectron Spectroscopy of Halomethanes. Effects of Electronegativity, Hardness, Charge Distribution, and Relaxation

et al. 2004

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Carbon 1s ionization energies have been measured for 12 halomethanes. These together with earlier measurements provide 27 compounds for investigating the relationship between core-ionization energies and the electronegativity and hardness of the halogens. The ionization energies correlate nearly linearly with the sum of the electronegativities of the halogens attached to the central carbon. Both electronegativity and hardness play important roles in determining the ionization energy, and it is found that the linear relationship between ionization energy and electronegativity arises from an interplay of the electronegativity and hardness of the halogens and the length and ionicity of the carbon-halogen bond.

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Section: Experimental Procedures and Experimental Resultsmentioning

confidence: 99%

Carbon 1s Photoelectron Spectroscopy of Halomethanes. Effects of Electronegativity, Hardness, Charge Distribution, and Relaxation

et al. 2004

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“…However, Δ E Fe 3d derives from differences in the effective charges of the metal centers ( ) in the two initial (ferrous) species. Such information can be derived from core ionization energies, which have been used extensively as a method of comparing charge density distributions in both organic − and inorganic systems. There should therefore be a relationship between E Fe 3d and the experimentally determined core E Fe 2p binding energy of the unrelaxed final state.…”

Section: Results and Analysismentioning

confidence: 99%

Electronic Structure Contributions to Electron-Transfer Reactivity in Iron−Sulfur Active Sites: 2. Reduction Potentials

Kennepohl

Solomon

2003

Inorg. Chem.

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This study utilizes photoelectron spectroscopy (PES) combined with theoretical methods to determine the electronic structure contributions to the large reduction potential difference between [FeCl(4)](2)(-)(,1)(-) and [Fe(SR)(4)](2)(-)(,1)(-) (DeltaE(0) approximately 1 V). Valence PES data confirm that this effect results from electronic structure differences because there is a similarly large shift in the onset of valence ionization between the two reduced species (DeltaI(vert) = 1.4 +/- 0.3 eV). Specific electronic contributions to DeltaI(vert) have been investigated and defined. Ligand field effects, which are often considered to be of great importance, contribute very little to DeltaI(vert) (DeltaE(LF) < -0.05 eV). By contrast, electronic relaxation, a factor that is often neglected in the analysis of chemical reactivity, strongly affects the valence ionization energies of both species. The larger electronic relaxation in the tetrathiolate allows it to more effectively stabilize the oxidized state and lowers its I(vert) relative to that of the chloride (DeltaE(rlx) = 0.2 eV). The largest contribution to the difference in redox potentials is the much lower effective charge () of the tetrathiolate in the reduced state, which results in a large difference in the energy of the Fe 3d manifold between the two redox couples (DeltaE(Fe)( )(3d) = 1.2 eV). This difference derives from the significantly higher covalency of the iron-thiolate bond, which decreases and significantly lowers its redox potential.

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“…The preferred site of attack by the proton is the nitrogen at any level of calculation, the energy difference being around 160 kJ mol -1 . The proton affinity of NH 2 Cl was estimated several years ago by Jolly and Bakke (795.0 kJ mol -1 ) and by Kollman and Rothenberg (856.9 kJ mol -1 ). The first value is in reasonable agreement with the value computed by us for the protonation of the nitrogen, while the second value seems to be somewhat overstimated.…”

Section: Resultsmentioning

confidence: 99%

Gas-Phase Chemistry of NH_xCl_y⁺. 1. Structure, Stability, and Reactivity of Protonated Monochloramine

Ricci

Rosi

1998

J. Phys. Chem. A

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The structure and the reactivity of gaseous NH3Cl+ ions obtained from direct protonation of aqueous monochloramine by CI/CH4 and from ionization of a Cl2 plasma containing trace amounts of ammonia have been investigated by FT-ICR mass spectrometry. The results characterized the NH3Cl+ ions arising from both experiments as having the NH3−Cl+ structure, consistent with the results of MO SCF calculations pointing to the higher basicity of the nitrogen than the chlorine atom of NH2Cl. The gas-phase basicity of monochloramine has been estimated to be 761 ± 5 kJ mol-1 from bracketing experiments according to the procedure based on the relationship between the efficiency and the standard free-energy difference of proton transfer. This value is consistent with those from theoretical calculations at the B3LYP and CCSD(T)/6-311++G(3df,3pd) level. In agreement with the protonation site, the NH3Cl+ ions behave as a protonating and chlorinating agent but addition is also observed.

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Prediction of core electron binding energies with a four-parameter equation

Cited by 26 publications

References 3 publications

Carbon 1s Photoelectron Spectroscopy of Halomethanes. Effects of Electronegativity, Hardness, Charge Distribution, and Relaxation

Carbon 1s Photoelectron Spectroscopy of Halomethanes. Effects of Electronegativity, Hardness, Charge Distribution, and Relaxation

Electronic Structure Contributions to Electron-Transfer Reactivity in Iron−Sulfur Active Sites: 2. Reduction Potentials

Gas-Phase Chemistry of NH_xCl_y⁺. 1. Structure, Stability, and Reactivity of Protonated Monochloramine

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Prediction of core electron binding energies with a four-parameter equation

Cited by 26 publications

References 3 publications

Carbon 1s Photoelectron Spectroscopy of Halomethanes. Effects of Electronegativity, Hardness, Charge Distribution, and Relaxation

Carbon 1s Photoelectron Spectroscopy of Halomethanes. Effects of Electronegativity, Hardness, Charge Distribution, and Relaxation

Electronic Structure Contributions to Electron-Transfer Reactivity in Iron−Sulfur Active Sites: 2. Reduction Potentials

Gas-Phase Chemistry of NHxCly+. 1. Structure, Stability, and Reactivity of Protonated Monochloramine

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Gas-Phase Chemistry of NH_xCl_y⁺. 1. Structure, Stability, and Reactivity of Protonated Monochloramine