Spectroscopic manifestations of structural shell filling in (benzene)n clusters, N = 1–20

Easter, David C.; El‐Shall, M. Samy; Hahn, M. Y.; Whetten, Robert L.

doi:10.1016/0009-2614(89)87247-1

Cited by 38 publications

(9 citation statements)

References 17 publications

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“…A red shift implies that the excited state is more tightly bound than the ground state, and a blue shift is associated with stronger interaction in the ground state. A red shift is usually observed in clusters where the dispersion energy is dominant due to the increase in the molecular polarizability in the excited state relative to the ground state. , For example, ring−ring interactions result in red shifts because dispersive forces are stronger for the more delocalized excited states, as in benzene and other aromatic clusters. , On the other hand, hydrogen bonding to the π-system results in a blue shift, which tends to increase with increasing the H-bond donating capacity of the solvent molecules …”

Section: Resultsmentioning

confidence: 99%

Resonant Two-Photon Ionization Spectroscopy of Styrene (Methanol)_nClusters,n= 1−9

et al. 2003

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Well-resolved spectra of styrene−methanol binary clusters SM n , with n = 1−9, have been obtained by the (one-color) resonant two-photon ionization technique using the resonance of styrene. The spectra reveal a rapid increase in complexity with the number of methanol molecules in the cluster, associated with van der Waals modes and isomeric forms. Two distinct isomers are identified for each of the clusters studied with the exception of SM4 and SM8. The progressive addition of methanol molecules to the SM complex leads to the formation of stable cyclic and branched cyclic methanol subclusters within the SM n clusters. The spectral shift of the cluster origin reflects the nature of the intermolecular interactions within the binary cluster. Blue shifts are observed for the SM, SM2, and SM3 clusters and are consistent with hydrogen bonding interactions between the OH groups and the styrene π-system. A remarkable switch in the spectral shift from blue to red is observed at the SM4 cluster and is consistent with the ring structure of the methanol tetramer. Evidence is provided for intracluster dissociative proton-transfer reactions within the S2M n + (n > 2) clusters that generate protonated methanol clusters. These reactions may explain the strong inhibition effects exerted by small concentrations of methanol on the cationic polymerization of styrene.

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Section: Resultsmentioning

confidence: 99%

Resonant Two-Photon Ionization Spectroscopy of Styrene (Methanol)_nClusters,n= 1−9

et al. 2003

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“…The dissociation behavior of van der Waals (vdW) complexes of aromatic molecules has been subject of extensive theoretical and experimental investigations. − Because of their small binding energy, the ionization of vdW complexes by one- or two-photon ionization is often accompanied by a simultaneous fragmentation when the excess energy above the adiabatic ionization energy (AIE) exceeds the dissociation energy. For that reason it is important to control the amount of energy deposited in the complex ion by the excitation process.…”

Section: Introductionmentioning

confidence: 99%

Dissociation of van der Waals Complexes in High Rydberg States Induced by Electric Fields

1997

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Due to its mass and energy selectivity, mass-analyzed threshold ionization spectroscopy provides information on the energetic position of the dissociation threshold of van der Waals complex cations. In this work we report the first observation of a shift of the dissociation threshold of van der Waals complexes in high Rydberg states induced by an applied electric field of several hundred V/cm. The detection of a ≈70 cm-1 shift is possible for fluorobenzene·Ar because of its high density of optically accessible vibrational states around the dissociation threshold at 568 cm-1. This shift is explained by a field-induced coupling between high and low Rydberg states of different series.

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“…It should be added that larger benzene clusters have also recieved considerable attention, , as well as the clusters of larger aromatic molecules such as naphthalene …”

Section: Bound State Properties: Structures and Potential Energy Sur...mentioning

confidence: 99%

Molecular Clusters: Structure and Dynamics of Weakly Bound Systems

1996

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Weakly bound atomic and molecular clusters can be viewed as finite-size “pieces” of the condensed phases of matter. From both the experimental and theoretical points of view, the finite size of these clusters is of great advantage in simplifying the system, permitting molecular level characterization of solvent effects on the solute spectroscopy and chemical reaction dynamics. In addition, the ability to vary the number of atoms or molecules in the cluster enables us to observe how its various structural and dynamical properties evolve with size, from those typical of isolated gas phase molecules toward the bulk limit. By far the most detailed information has been obtained for binary complexes, where the issues of interest are the determination of intermolecular potential energy surfaces and understanding the vibrational dynamics of these complexes. Considerable progress has also been made in the characterization of higher-order complexes, which provide information on many-body interactions and more realistically approximate solvated systems. Since the breadth of this field precludes a complete review, we attempt here only to give some examples that illustrate the important issues and convey some of the excitement.

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Spectroscopic manifestations of structural shell filling in (benzene)n clusters, N = 1–20

Cited by 38 publications

References 17 publications

Resonant Two-Photon Ionization Spectroscopy of Styrene (Methanol)_nClusters,n= 1−9

Resonant Two-Photon Ionization Spectroscopy of Styrene (Methanol)_nClusters,n= 1−9

Dissociation of van der Waals Complexes in High Rydberg States Induced by Electric Fields

Molecular Clusters: Structure and Dynamics of Weakly Bound Systems

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Spectroscopic manifestations of structural shell filling in (benzene)n clusters, N = 1–20

Cited by 38 publications

References 17 publications

Resonant Two-Photon Ionization Spectroscopy of Styrene (Methanol)nClusters,n= 1−9

Resonant Two-Photon Ionization Spectroscopy of Styrene (Methanol)nClusters,n= 1−9

Dissociation of van der Waals Complexes in High Rydberg States Induced by Electric Fields

Molecular Clusters: Structure and Dynamics of Weakly Bound Systems

Contact Info

Product

Resources

About

Resonant Two-Photon Ionization Spectroscopy of Styrene (Methanol)_nClusters,n= 1−9

Resonant Two-Photon Ionization Spectroscopy of Styrene (Methanol)_nClusters,n= 1−9