Excited state energetics of aniline-rare-gas van der Waals complexes

Amirav, Aviv; Even, U.; Jortner, Joshua; Dick, Bernhard

doi:10.1080/00268978300101641

Cited by 44 publications

(20 citation statements)

References 29 publications

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“…The main fluorescence peak due to the n = 2 complex appears at -106 cm -~ from the free aniline transition, i.e. twice the n = I spectral shift, which confirms the equivalence of the sites occupied by the first two Argon atoms, above and below the plane of the Aniline ring, as already discussed by other authors [9,,Io]. However no other narrow feature which could be attributed to clusters with n > 3 can be observed in the fluorescence spectra.…”

Section: / Tsupporting

confidence: 80%

Microsolvation of aniline by argon: fluorescence excitation and two photon resonant ionization of An — Arn in a supersonic jet

Bréchignac¹,

Coutant²

1989

Z Phys D - Atoms, Molecules and Clusters

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Section: / Tsupporting

confidence: 80%

Microsolvation of aniline by argon: fluorescence excitation and two photon resonant ionization of An — Arn in a supersonic jet

Bréchignac¹,

Coutant²

1989

Z Phys D - Atoms, Molecules and Clusters

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“…Figure 3 shows the associated fluorescence excitation spectrum in the lowest energy spectral region. The polarizability (19) of CH, is 0.29 x lo-" cm3 which is greater than that of Ar and thus, based on the above discussion, dispersion interactions again appear to be the major source of the excited state stabilization. This is illus- Can 4.…”

Section: B Molecular Itzteractions Of Itzdole With Selected Halomethmentioning

confidence: 99%

“…to the red of the associated bare molecule transition). Amirav et al (19) have shown that for the aniline-Ar van der Waals system, the contribution of dipole -induced dipole interactions to the total excited spectral shift is approximately 5%. The simplest expression for this dipole -induced dipole stabilization energy using a point dipole approximation is given by (16), where p is the dipole moment of the polarizer (in this case indole) and a is the polarizability of the complexing partner in the van der Waals molecule.…”

Section: B Molecular Itzteractions Of Itzdole With Selected Halomethmentioning

confidence: 99%

Supersonic beam investigations of indole and indole–halomethane complexes: intermolecular interactions

Hager¹,

Wallace²

1985

Can. J. Chem.

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. Can. J. Chem. 63, 1502Chem. 63, (1985. We report the findings of a supersonic beam investigation of the I : 1 gas phase complexes of indole with various halomethanes. The unique environment of the supersonic jet provides a method by which the pairwise intermolecular interactions of these complexes can be studied without the complications of condensed media effects. The behavior of argon and methane van der Waals molecules is described first in order to.provide examples of simple dispersive interactions. These are then contrasted with complexing species such as CF, and CCI, where repulsive interactions offset the stabilization due to dispersive and dipole -induced dipole forces. Finally, we show that the interaction between the probe molecule and CHC13 and CH2CI2 is apparently hydrogen bonding with the indole .rr electronic system. The implications of these intermolecular interactions on the area of general anesthesia are discussed in terms of a picture in which both the hydrophobic and polar portions of cell membrane may be reversibly affected. [Traduit par le journal]

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“…Ar, were exhibited, revealing two spectral features; (3) the spectral features of the So + SIX transition are blue shifted, being located at Sv = + 8 ? 1 cm-I; (4) For personal use only. spectroscopic evidence for the existence of a single energetically stable structure of the H2P-Arl complex.…”

Section: Discussionmentioning

confidence: 99%

Electronic excitations of the free-base porphine–Ar van der Waals complex

Even¹,

Jortner²,

Berkovitch‐Yellin³

1985

Can. J. Chem.

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This paper is dedicated to Professor Carnille S a r~d o ron the occasion of his 65th birthday Uzr EVEN, JOSHUA JORTNER, and ZIVA BERKOVITCH-YELLIN. Can. J. Chem. 63, 2073Chem. 63, (1985.In this paper we report on the excited-state energetics of the two lowest-lying intravalence electronic excitations So -+ S," and So -+ S l y of a large van der Waals complex, consisting of Ar bound to free-base porphine (HIP). HIP. Ar,, complexes were synthesized and interrogated by laser-induced fluorescence in seeded supersonic expansions of Ar and He/Ar. Diagnostic methods, which were based on the dependence of the intensity of the spectral features on the stagnation pressure and on spectroscopy in He(99%)/Ar(l%) mixtures, were utilized for the identification of the vibrationless electronic excitations of H,P.Ar,. The spectroscopic data were supplemented by model calculations of the potential surface, which demonstrate that the single equilibrium configuration of H2P.RI (R = Ne, Ar, Kr, and Xe) corresponds to the R atom being located at the twofold symmetry axis perpendicular to the porphyrin ring. While the intense S,, -+ S l y transition of HzP. Ar, exhibits a red, dispersive, microscopic solvent shift (6v = -24 cm-I), the So -+ SI" transition is characterized by a blue microscopic spectral shift (6v = + 8 cm-I), which provides a unique example for excited-state destabilization, originating from intramolecular configurational changes induced by van der Waals binding in a large complex. .Ar1, on a utilisC des mCthodes d'kvaluation qui sont basCes sur la relation qui existe entre I'intensitC des caractCristiques spectrales et la pression de stagnation ainsi que sur la spectroscopie dans des mClanges 2 99% He/]% Ar. On a utilisC les donnCes spectrales de concert avec des calculs modkles de la surface de potentiel qui dimontrent que la seule configuration dlCquilibre du H2P.RI (R = Ne, Ar, Kr et Xe) correspond a celle dans laquelle l'atome R se trouve au niveau de I'axe de symCtrie binaire qui est perpendiculaire au noyau de la porphyrine. Alors que la transition intense So + Sly du H,P.Ar, prCsente un dCplacement microscopique dC au solvant qui soit dispersif et qui se dCplace vers le rouge (6v = -24 cm-I), la transition So -+ S," est caractCrisCe par un dCplacement spectral microscopique vers le bleu (6v = + 8 cm-I); ces rksultats correspondent a un exemple unique de d~stabilisation de 1'Ctat excitC provenant de changements configurationnels intramolCculaires qui sont induits par un couplage de van der Waals dans un vaste complexe.[Traduit par le journal]

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Excited state energetics of aniline-rare-gas van der Waals complexes

Abstract: Aniline-Nen and aniline-Arn (n = 1 and 2) complexes were synthesized in continuous and in pulsed supersonic expansions and interrogated by laserinduced fluorescence. Information on the formation kinetics and excited state energetics was obtained.

Cited by 44 publications

References 29 publications

Microsolvation of aniline by argon: fluorescence excitation and two photon resonant ionization of An — Arn in a supersonic jet

Microsolvation of aniline by argon: fluorescence excitation and two photon resonant ionization of An — Arn in a supersonic jet

Supersonic beam investigations of indole and indole–halomethane complexes: intermolecular interactions

Electronic excitations of the free-base porphine–Ar van der Waals complex

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