Anwendungen der Zero-Kinetic-Energy(ZEKE)-Photoelektronenspektroskopie in der Chemie

Müller‐Dethlefs, Klaus; Schlag, E. W.

doi:10.1002/(sici)1521-3757(19980518)110:10<1414::aid-ange1414>3.0.co;2-2

Cited by 9 publications

(15 citation statements)

References 170 publications

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“…Accurate IEs of molecules are available through ZEKE photoelectron spectroscopy, [18][19][20] a technique based on the pulsed field ionization of high-lying Rydberg states. In this technique a laser is tuned across an ionization threshold and an electron signal appears whenever the laser is in resonance with molecular Rydberg states of nϷ200, converging to an ionic state.…”

Section: ͓S0021-9606͑00͒02006-7͔mentioning

confidence: 99%

“…In this technique a laser is tuned across an ionization threshold and an electron signal appears whenever the laser is in resonance with molecular Rydberg states of nϷ200, converging to an ionic state. While a large number of stable molecules and molecular clusters have been successfully studied by this technique, 20 ZEKE spectra have only been reported for two hydrocarbon radicals so far, methyl, 21 CH 3 , and benzyl, 22 C 6 H 5 CH 2 . One reason for the lack of data on radicals is the difficulty of generating them cleanly at high number density.…”

Section: ͓S0021-9606͑00͒02006-7͔mentioning

confidence: 99%

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The zero kinetic energy photoelectron spectrum of the propargyl radical, C3H3

Gilbert¹,

Pfab²,

Fischer³

et al. 2000

The Journal of Chemical Physics

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We report the zero kinetic energy photoelectron spectrum of the propargyl radical, C3H3. From the spectrum an ionization energy of 69 953±10 cm−1 (8.673 eV) is deduced. Vibrational frequencies are obtained for the totally symmetric normal modes of the propargyl cation, as well as some combination and overtone bands. Both the frequencies and the relative intensities agree well with the predictions from recent ab initio calculations.

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Section: ͓S0021-9606͑00͒02006-7͔mentioning

confidence: 99%

Section: ͓S0021-9606͑00͒02006-7͔mentioning

confidence: 99%

The zero kinetic energy photoelectron spectrum of the propargyl radical, C3H3

Gilbert¹,

Pfab²,

Fischer³

et al. 2000

The Journal of Chemical Physics

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“…[2] While a number of theoretical and time-resolved studies have contributed to our mechanistic understanding of this problem, [1] there is currently little spectroscopic information available for cationic amides. Here we present initial results that indicate that zero electron kinetic energy (ZEKE) spectroscopy, [5,6] a highresolution variant of photoelectron spectroscopy, may represent a powerful technique for obtaining vibrationally resolved spectra of cationic amides and model peptides. Here we present initial results that indicate that zero electron kinetic energy (ZEKE) spectroscopy, [5,6] a highresolution variant of photoelectron spectroscopy, may represent a powerful technique for obtaining vibrationally resolved spectra of cationic amides and model peptides.…”

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confidence: 99%

“…[3,4] Basic questions regard the preference for cis or trans conformations and barrier heights for interconversion. Here we present initial results that indicate that zero electron kinetic energy (ZEKE) spectroscopy, [5,6] a highresolution variant of photoelectron spectroscopy, may represent a powerful technique for obtaining vibrationally resolved spectra of cationic amides and model peptides. Spectra are presented for both the cis and trans isomers of formanilide, an aromatic molecule with an amide side chain.…”

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confidence: 99%

“…The Dn 0 propensity rule [5] and parity considerations were employed to assign each of the strong vibrational features in the ZEKE spectra of cis-formanilide (Table 1). Several of the ZEKE spectra display excitation of features with both s and a parity due to the cation being accessed via S 1 bands corresponding to overlapping S 1 2 S 0 transitions with different parities.…”

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ZEKE Photoelectron Spectroscopy of the cis and trans Isomers of Formanilide

Ullrich

Tarczay

Tong

et al. 2002

Angew. Chem. Int. Ed.

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Spectroscopic characterization of cationic amides: ZEKE photoelectron spectroscopy has been successfully applied to isomers of the model peptide formanilide. The spectra indicate that significant charge delocalization occurs from the aromatic ring to the side chain in the ion. The picture shows the spectrum of the trans isomer together with the side‐chain in‐plane bending and amide stretching modes that are associated with the B′ and Σ′ bands. IE=ionization energy.

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ZEKE Photoelectron Spectroscopy of thecis andtrans Isomers of Formanilide

et al. 2002

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Cationic states are involved in long-range charge transfer in polypeptides, [1] an area of intense chemical interest. [2] While a number of theoretical and time-resolved studies have contributed to our mechanistic understanding of this problem, [1] there is currently little spectroscopic information available for cationic amides. [3,4] Basic questions regard the preference for cis or trans conformations and barrier heights for interconversion. Here we present initial results that indicate that zero electron kinetic energy (ZEKE) spectroscopy, [5,6] a highresolution variant of photoelectron spectroscopy, may represent a powerful technique for obtaining vibrationally resolved spectra of cationic amides and model peptides. Spectra are presented for both the cis and trans isomers of formanilide, an aromatic molecule with an amide side chain. The aromatic group provides a convenient chromophore, while significant charge delocalization occurs from the aromatic ring to the functional group in the cation, so that formanilide is a useful model system for studying the properties of cationic amides.Local-minimum geometric structures of the neutral (S 0 ) and cationic (D 0 ) isomers of formanilide obtained from MP2(fc)/ 6-31G* ab initio calculations are presented in Figure 1. [7] For trans-formanilide, the calculations predict that the molecule Figure 1. Optimized structures of the neutral (S 0 ) and cationic (D 0 ) isomers of formanilide at the MP2(fc)/6-31G* level of theory illustrating the ionization-induced geometry changes. Total energies are given relative to the energy of the S 0 state of trans-formanilide (À 399.693829 Hartree).[9] More recently, aerobic intramolecular oxidative amination has been achieved with a [Pd(OAc) 2 ]/O 2 /DMSO catalyst system that lacks a cocatalyst: a) R.

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Anwendungen der Zero-Kinetic-Energy(ZEKE)-Photoelektronenspektroskopie in der Chemie

Cited by 9 publications

References 170 publications

The zero kinetic energy photoelectron spectrum of the propargyl radical, C3H3

The zero kinetic energy photoelectron spectrum of the propargyl radical, C3H3

ZEKE Photoelectron Spectroscopy of the cis and trans Isomers of Formanilide

ZEKE Photoelectron Spectroscopy of thecis andtrans Isomers of Formanilide

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