Photoelectron spectra of molecules. Part 12. Vinyl, allyl, and phenyl ethers and sulphides

Mölder, U.; Pikver, R.; Koppel, Indrek; Burk, Peeter; Koppel, Ilmar A.

doi:10.1016/s0166-1280(01)00736-9

Cited by 10 publications

(9 citation statements)

References 65 publications

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“…This is the reason why the KS eigenfunctions

ϕ_{i}^{} true(\overset{r}{true} true)

are interpreted as approximate relaxed Dyson orbitals, and the respective KS orbital energies ε i are interpreted as approximate relaxed ionization potentials . The validity of this statement has been verified by several authors on a number of atoms and simple molecules . Thus, the ionization processes in a molecule can be more successfully approximated using DFT than Koopmans’ theorem within the HF framework.…”

Section: Introductionmentioning

confidence: 94%

Application of DFT for the modeling of the valence region photoelectron spectra of boron and d‐element complexes and macromolecules

Osmushko

Vovna

Tikhonov

et al. 2015

Int J of Quantum Chemistry

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Using density functional theory (DFT) in conjunction with ultraviolet (UPS) and X‐ray photoelectron spectroscopy (XPS), we investigated a number of complexes and macromolecules. We have shown on a large set of UPS, XPS, and DFT data that the calculated Kohn–Sham energies of organic and metalorganic complexes can be used as approximate ionization energies (IEs). It is possible to evaluate IEs with an accuracy of 0.1 eV with the density functional approximation (DFA) defect approach. This method has been successfully tested on a large number of boron β‐diketonates and d‐metal chelate and sandwich complexes. We interpreted the bands in the valence region of the XP spectra of macromolecular organosilicon compounds in the solid state by taking into account the density of states and the ionization cross‐sections. According to DFT calculation results, the one‐electron states in the valence region of the model compounds correlate with the positions of the spectral band maxima. © 2015 Wiley Periodicals, Inc.

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“…This is the reason why the KS eigenfunctions

ϕ_{i}^{} true(\overset{r}{true} true)

Section: Introductionmentioning

confidence: 94%

Application of DFT for the modeling of the valence region photoelectron spectra of boron and d‐element complexes and macromolecules

Osmushko

Vovna

Tikhonov

et al. 2015

Int J of Quantum Chemistry

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“…Time-resolved photoelectron spectra of EVE, PVE, and 2PrVE upon excitation at 200 nm (6.2 eV) and ionization at 267 nm (4.65 eV) are shown in Figure a–c. The vertical ionization potential of EVE is 8.83 eV . Therefore, it is expected that the energy cutoff for experiments with a one-photon pump and a one-photon probe [1,1′] lies at a photoelectron kinetic energy of 10.85 eV – 8.83 eV = 2.02 eV.…”

Section: Resultsmentioning

confidence: 99%

Influence of Alkoxy Groups on the Photoinduced Dynamics of Organic Molecules Exemplified on Alkyl Vinyl Ethers

Schalk

Stenrup²,

Geng

et al. 2015

J. Phys. Chem. A

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A series of different alkyl vinyl ethers is investigated to decipher the possible reaction channels upon photoexcitation to the π3s-Rydberg and the ππ*-valence state at 200 nm using time-resolved photoelectron spectroscopy and on-the-fly time-dependent density functional theory dynamics simulations. The results indicate two possible relaxation pathways: (1) a radiationless decay through the ππ*-state back to the ground state via torsion of the C═C double bond, in accordance with the dynamics found in ethylene; and (2) a fast dissociation of the C-O bond between the alkyl and the vinoxy group in the πσ*-state. The latter state can be accessed only after excitation to the π3s-Rydberg state (quantum yield of ∼50% according to the dynamics simulations). Additionally, the excited state barrier leading to formation of a vinyl radical was found to be too high to be crossed. These results indicate that the dynamics of ethers crucially depend on the excitation wavelength and that the πσ*-state constitutes an important competitive reaction channel that leads to dissociation of the molecules.

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“…35 Allyl ribofuranoside (AR) was prepared by O-glycosidation of D-ribose in allyl alcohol (Scheme 3). 19 AR can be further converted into the cyclic acetal AIR by reacting the two hydroxylic groups in cis-position at carbons C2 and C3 with acetone under acid catalysis. 18 The second sugar-derived monomer exhibits distinct physical and chemical properties, particularly as a consequence of reduced aptitude for H-bonding.…”

Section: Resultsmentioning

confidence: 99%

“…19 In the presence of molecules exhibiting sufficient electron affinity, the formation of stable charge transfer complex is far less favorable than in the case of vinyl ethers, with their specific conjugation of the nonbonding electrons with the ethylenic π system.…”

Section: Introductionmentioning

confidence: 99%

Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

et al. 2009

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The free radical copolymerization of allyl ribosides with diethyl fumarate and maleate was investigated for evaluating the potential of donor-acceptor type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends was conducted in solution as well as in liquid films of bulk reactants. Infrared spectroscopy was used to monitor the consumption of the allylic donor monomer and of the butenedicarboxylate acceptor monomers. The method allowed examining the influence of the nature of the monomer pair and of their relative concentration on the kinetic profiles. Comparison with reference vinyl ether monomers confirmed the expected lower reactivity of the blends containing allylic derivatives. SEC and NMR analysis supported the occurrence of degradative chain transfer during the reactions involving allylic monomers. However, allyl derivatives of glycerol as well as O-allyl ribosides were shown to undergo polymerization with high conversion of both monomers when blended in appropriate molar ratios.

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Photoelectron spectra of molecules. Part 12. Vinyl, allyl, and phenyl ethers and sulphides

Cited by 10 publications

References 65 publications

Application of DFT for the modeling of the valence region photoelectron spectra of boron and d‐element complexes and macromolecules

Application of DFT for the modeling of the valence region photoelectron spectra of boron and d‐element complexes and macromolecules

Influence of Alkoxy Groups on the Photoinduced Dynamics of Organic Molecules Exemplified on Alkyl Vinyl Ethers

Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

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