Photoelectron ionization potentials

Fig. 38. Photoelectron ionization potential correlation diagram for ketene and thioketene...

Cederbaum L S and Domcke W 1977 Theoretical aspects of ionization potentials and photoelectron spectroscopy a Green s function approach Adv. Chem. Phys. 36 205-344 Oddershede J 1987 Propagator methods Adv. Chem. Phys. 69 201-39... 

Ultraviolet photoelectron spectroscopy allows the determination of ionization potentials. For thiazole the first experimental measurement using this technique was preformed by Salmona et al. (189) who later studied various alkyl and functional derivatives in the 2-position (190,191). Substitution of an hydrogen atom by an alkyl group destabilizes the first ionization potential, the perturbation being constant for tso-propyl and heavier substituents. Introduction in the 2-position of an amino group strongly destabilizes the first band and only slightly the second. 

Mass spectrometry can be used to determine ionization potentials by the method of Lossing (283). The values obtained can be compared with those found by photoelectron spectroscopy and those calculated by CNDO/S (134) or ab initio (131) methods using the Koopman theorem approximation. The first and second, ionization potentials concern a ir... 

In this method, photons of an energy well in excess of the ionization potential are directed onto a molecule. The photoelectron spectrum which results allows assessment of the energies of filled orbitals in the molecule, and thus provides a characterization of a molecule. Comparisons between photoelectron spectra of related compounds give structural information, for example, on the tautomeric structure of a compound by comparison of its spectrum with those of models of each of the fixed forms. 

The vertical ionization potentials from the photoelectron spectra of some thiirane and thiirene derivatives are given in Table 3. A Walsh localized scheme of bonding is generally preferred. There is a strong hyperconjugative interaction in thiirene 1,1-dioxides between the occupied C=C tt-MO and the occupied SO2 pure sulfur d-AO. Thiirene oxides are suggested to be less aromatic than cyclopropenones and tropone. 

Photoelectron spectroscopic studies show that the first ionization potential (lone pair electrons) for cyclic amines falls in the order aziridine (9.85 eV) > azetidine (9.04) > pyrrolidine (8.77) >piperidine (8.64), reflecting a decrease in lone pair 5-character in the series. This correlates well with the relative vapour phase basicities determined by ion cyclotron resonance, but not with basicity in aqueous solution, where azetidine (p/iTa 11.29) appears more basic than pyrrolidine (11.27) or piperidine (11.22). Clearly, solvation effects influence basicity (74JA288). 

Trioxanes bond angles, 3, 949 bond lengths, 3, 949 H NMR, 3, 952 ionization potential, 3, 959 IR spectra, 3, 956 photoelectron spectroscopy, 3, 959 radical cations... 

The ionization potentials of some substituted noibomadienes have been measured by photoelectron spectroscopy. The values which pertain to the n orbitals are shown ... 

Unlike the stable molecule N2O, the sulfur analogue N2S decomposes above 160 K. In the vapour phase N2S has been detected by high-resolution mass spectrometry. The IR spectrum is dominated by a very strong band at 2040 cm [v(NN)]. The first ionization potential has been determined by photoelectron spectroscopy to be 10.6 eV. " These data indicate that N2S resembles diazomethane, CH2N2, rather than N2O. It decomposes to give N2 and diatomic sulfur, S2, and, hence, elemental sulfur, rather than monoatomic sulfur. Ab initio molecular orbital calculations of bond lengths and bond energies for linear N2S indicate that the resonance structure N =N -S is dominant. 

Ghosh and Almlof published many articles discussing the XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectra) and the corresponding ionization potentials of porphyrins using high-level calculations. Tliese topics are indirectly related to the tautomerism of porphyrins (for an example see 94IC6057 and 95JA4691). 

The most evident of these is the marked stability of radical cations formed in an aprotic medium by the oxidation of compounds where the first ionization potential (in the sense of photoelectron spectroscopy) is for the removal of an electron from a non-bonding orbital, e. g. thianthrene... 

Figure 7. The photoelectron spectrum of formaldehyde with the data on adiabatic ionization potentials. The fourth potential can be determined only at higher resolutions. [From (103) by permission of D. W. Turner and the publishing house].

Even the photoelectron spectroscopy of closed-shell molecules is valuable for the physical chemistry of radicals because a difference between the nth and the first adiabatic ionization potentials determines the excitation energy in a radical cation for a transition from the ground doublet state to the (n — 1) excited doublet state. 

The photoelectron spectrum of selenophene vapor down to 1350 A has been studied. By analogy with the other heterocyclic derivatives, Rydberg-type transitions occur, leading to the first ionization potential of the molecule.23... 

An alternative measure of the electron-donor properties is obtained from the energetics of electron detachment in the gas phase the ionization potentials (IP) of many organic donors have been experimentally determined from the photoelectron spectra obtained by their photoionization in the gas phase. Thus, the values of the ionization potential IP differ from the oxidation potential x by solvation,66 i.e.,... 

Various theoretical methods (self-consistent field molecular orbital (SCF-MO) modified neglect of diatomic overlap (MNDO), complete neglect of differential overlap (CNDO/2), intermediate neglect of differential overlap/screened approximation (INDO/S), and STO-3G ab initio) have been used to calculate the electron distribution, structural parameters, dipole moments, ionization potentials, and data relating to ultraviolet (UV), nuclear magnetic resonance (NMR), nuclear quadrupole resonance (NQR), photoelectron (PE), and microwave spectra of 1,3,4-oxadiazole and its derivatives <1984CHEC(6)427, 1996CHEC-II(4)268>. 

Extensive discussion on the ionization potentials of 1,2,5-thiadiazole and its derivatives can be found in CHEC(1984) and CHEC-II(1996) <1984CHEC(6)513, 1996CHEC-II(4)355>. Hel photoelectron spectroscopy, inner-shell electron energy loss spectroscopy involving the S2p, S2s, Cls and Nls edges, and Sis synchrotron radiation photoabsorption spectroscopy were used to probe the occupied and unoccupied valence levels of benzothiadiazole 2 <1991MI165>. 

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