Investigation of charge localization and charge delocalization in model molecules by multiphoton ionization photoelectron spectroscopy and DFT calculations

Weinkauf, R.; Lehrer, F.; Schlag, E. W.; Metsala, Andrus

doi:10.1039/b001092h

Cited by 63 publications

(122 citation statements)

References 43 publications

(14 reference statements)

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“…lished recently by Weinkauf et al 34 The absorption of several photons in the 2-PE cation is not expected for the small laser intensities that were used. The spectrum in Fig.…”

Section: A Low-resolution Spectrummentioning

confidence: 93%

Specific and nonspecific interactions in a molecule with flexible side chain: 2-phenylethanol and its 1:1 complex with argon studied by high-resolution UV spectroscopy

Chervenkov

Karaminkov

Braun

et al. 2006

The Journal of Chemical Physics

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Using high-resolution resonance-enhanced two-photon ionization spectroscopy in combination with genetic-algorithm-based computer-aided rotational fit analysis and ab initio quantum chemistry calculations we determined the conformational structure and transition moment orientation in 2-phenylethanol and its 1:1 clusters with argon. The results clearly demonstrate that the gauche structure of 2-phenylethanol, which is stabilized by the intramolecular pi-hydrogen bond between the folded side chain and the benzene ring, is the most abundant in the cold molecular beam. In this conformer the transition moment is rotated by 18 degrees from the short axis of the aromatic ring. Two distinct 1:1 complexes of 2-phenylethanol with argon in a cis- and trans-configuration with respect to the side chain have been found. Employing the Kraitchman [Am. J. Phys. 21, 17 (1953)] analysis we have found that the structure of the 2-phenylethanol moiety and the orientation of the transition moment do not change after the complexation with argon within the experimental accuracy. From the measured band intensities we conclude that in addition to the dispersion interaction of the argon atom with the aromatic ring a hydrogen-bond-type interaction with the terminal -OH group of the side chain stabilizes the cis-structure of the 1:1 complex of 2-phenylethanol with argon.

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“…lished recently by Weinkauf et al 34 The absorption of several photons in the 2-PE cation is not expected for the small laser intensities that were used. The spectrum in Fig.…”

Section: A Low-resolution Spectrummentioning

confidence: 93%

Specific and nonspecific interactions in a molecule with flexible side chain: 2-phenylethanol and its 1:1 complex with argon studied by high-resolution UV spectroscopy

Chervenkov

Karaminkov

Braun

et al. 2006

The Journal of Chemical Physics

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“…In particular, the interaction between the aromatic ring and the nearby OH group, evidenced by IR spectroscopy in the related benzyl alcohol molecule 11,12 is probably different in the neutral and the ion. Such a large neutral to cation geometry change in the geometry of a OH-bearing substituent has also been deduced from the photoelectron spectrum of 2-phenylethanol 13 and the ZEKE spectrum of benzylalcohol.…”

Section: Petoh/butan-2-ol Complexes Fragmentation Thresholdsmentioning

confidence: 96%

Spectroscopic studies of enantiomeric discrimination in jet‐cooled chiral complexes

et al. 2001

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Van der Waals complexes formed between chiral molecules in the isolated gas phase were studied by combining supersonic expansion techniques with laser spectroscopy. The weakly bound diastereoisomers formed between a chiral secondary alcohol, butan-2-ol, and a chiral aromatic derivative such as 2-naphthyl-1-ethanol or 1-phenylethanol used as a resolving agent were discriminated on the basis of the spectral shifts of the UV S(0)-S(1) transition of the chromophore. Ground-state depletion spectroscopy (hole burning) has shown that, while only one structure was detected for the 1-phenylethanol/butan-2-ol homochiral complex, the heterochiral complex is trapped in the jet under two different conformations. Two isomers have also been shown for each diastereoisomeric pair of the 2-naphthyl-1-ethanol/butan-2-ol complexes. Using a semiempirical potential model, these isomeric forms were related to calculated structures which exhibit a folded or extended geometry depending on the solvent conformation (anti or gauche). The relative binding energy of the complexes involving R-1-phenylethanol and R- or S-butan-2-ol were obtained from fragmentation threshold measurements following two-color photoionization. Comparison of the diastereoisomers exhibiting a similar spectral signature shows that the homochiral pair is more stable than the heterochiral one by about 0.7 kcal/mol. The fragmentation threshold has been shown to depend on the jet-cooled isomer and this result addresses the role of conformational control in enantioselective interactions.

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“…According to the well-known principle of "charge localization", the surplus charge is localized at the site with the lowest ionization energy (Weinkauf et al, 2000). Delocalization of charge affects internal properties of the molecule (such as optical and vibrational spectra) and its interaction with a polar environment, in particular, hydrogen bonding and solvation energy (Cuming et al, 1977).…”

Section: Introductionmentioning

confidence: 99%

Role of charge screening and delocalization for lipophilic cation permeability of model and mitochondrial membranes

Trendeleva¹,

Sukhanova²,

Рогов³

et al. 2013

Mitochondrion

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Investigation of charge localization and charge delocalization in model molecules by multiphoton ionization photoelectron spectroscopy and DFT calculations

Cited by 63 publications

References 43 publications

Specific and nonspecific interactions in a molecule with flexible side chain: 2-phenylethanol and its 1:1 complex with argon studied by high-resolution UV spectroscopy

Specific and nonspecific interactions in a molecule with flexible side chain: 2-phenylethanol and its 1:1 complex with argon studied by high-resolution UV spectroscopy

Spectroscopic studies of enantiomeric discrimination in jet‐cooled chiral complexes

Role of charge screening and delocalization for lipophilic cation permeability of model and mitochondrial membranes

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