Intermolecular vibronic spectroscopy of small Van Der Waals clusters: phenol- and aniline-(argon)2 complexes

Schmidt, M.; Mons, Michel; Calvé, J. Le

doi:10.1007/bf01437671

Cited by 30 publications

(28 citation statements)

References 8 publications

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“…Moreover, spectroscopic evidence for the geometric structure of neutral phenol-Ar 2 is scarce and not unambiguous as it relies on vibrationally resolved spectra only. 10,13,25,35 Recent holeburning spectra of phenol-Ar n with n = 1 and 2 demonstrated that all spectral features observed in the S 1 ← S 0 REMPI spectra indeed arise from single isomers in the molecular beam expansion, which have been assigned to -bonded structures for both n = 1 and n = 2. The refined analysis of the intermolecular vibrational structure observed for phenol-Ar 2 was, however, compatible with both a ͑1 ͉ 1͒ and a ͑2 ͉ 0͒ structure.…”

Section: Introductionmentioning

confidence: 99%

The structure of phenol-Arn (n=1,2) clusters in their S and S1 states

Kalkman¹,

Brand²,

Vu³

et al. 2009

The Journal of Chemical Physics

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The structures of the van der Waals bonded complexes of phenol with one and two argon atoms have been determined using rotationally resolved electronic spectroscopy of the S(1)<--S(0) transition. The experimentally determined structural parameters were compared to the results of quantum chemical calculations that are capable of properly describing dispersive interactions in the clusters. It was found that both complexes have pi-bound configurations, with the phenol-Ar(2) complex adopting a symmetric (1mid R:1) structure. The distances of the argon atoms to the aromatic plane in the electronic ground state of the n=1 and n=2 clusters are 353 and 355 pm, respectively. Resonance-enhanced multiphoton ionization spectroscopy was used to measure intermolecular vibrational frequencies in the S(1) state and Franck-Condon simulations were performed to confirm the structure of the phenol-Ar(2) cluster. These were found to be in excellent agreement with the (1mid R:1) configuration.

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Section: Introductionmentioning

confidence: 99%

The structure of phenol-Arn (n=1,2) clusters in their S and S1 states

Kalkman¹,

Brand²,

Vu³

et al. 2009

The Journal of Chemical Physics

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“…34 In the following, we will briefly review the knowledge available for PhOH -Ar n clusters. The analysis of electronic and vibrational transition frequencies in REMPI, 23,[35][36][37][38][39] PIE, 23 IR dip, 40,41 and stimulated Raman 42 spectra demonstrate that PhOH -Ar n with n = 1 and 2 display bonding in the neutral electronic ground and first excited state ͑S 0 , S 1 ͒, whereby PhOH -Ar 2 was concluded to have a sandwich structure, in which both Ar atoms are located on opposite sides of the aromatic ring. 23 In particular, the OH frequency is a sensitive probe for the -bound and H-bound structure, because the latter one will lead to a characteristic redshift of the vibrational frequency upon formation of the H bond.…”

Section: Introductionmentioning

confidence: 99%

IR signature of the photoionization-induced hydrophobic→hydrophilic site switching in phenol-Arn clusters

Ishiuchi

Sakai

Tsuchida

et al. 2007

The Journal of Chemical Physics

139

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IR spectra of phenol-Arn (PhOH-Arn) clusters with n=1 and 2 were measured in the neutral and cationic electronic ground states in order to determine the preferential intermolecular ligand binding motifs, hydrogen bonding (hydrophilic interaction) versus pi bonding (hydrophobic interaction). Analysis of the vibrational frequencies of the OH stretching motion, nuOH, observed in nanosecond IR spectra demonstrates that neutral PhOH-Ar and PhOH-Ar2 as well as cationic PhOH+-Ar have a pi-bound structure, in which the Ar atoms bind to the aromatic ring. In contrast, the PhOH+-Ar2 cluster cation is concluded to have a H-bound structure, in which one Ar atom is hydrogen-bonded to the OH group. This pi-->H binding site switching induced by ionization was directly monitored in real time by picosecond time-resolved IR spectroscopy. The pi-bound nuOH band is observed just after the ionization and disappears simultaneously with the appearance of the H-bound nuOH band. The analysis of the picosecond IR spectra demonstrates that (i) the pi-->H site switching is an elementary reaction with a time constant of approximately 7 ps, which is roughly independent of the available internal vibrational energy, (ii) the barrier for the isomerization reaction is rather low(<100 cm(-1)), (iii) both the position and the width of the H-bound nuOH band change with the delay time, and the time evolution of these spectral changes can be rationalized by intracluster vibrational energy redistribution occurring after the site switching. The observation of the ionization-induced switch from pi bonding to H bonding in the PhOH+-Ar2 cation corresponds to the first manifestation of an intermolecular isomerization reaction in a charged aggregate.

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“…In the past ten years, clusters containing an aromatic molecule and several rare gas atoms have been studied by a number of groups [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Two dominant motivations underly the great interest in these systems.…”

Section: Introductionmentioning

confidence: 99%

Resonant two-photon two-color photoionization (R2P2CI) spectra of aniline-Ar n clusters: Isomer strutures and solvent shifts

Hermine

Parneix

Coutant

et al. 1992

Z Phys D - Atoms, Molecules and Clusters

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We present resonant two-photon two-color photoionization (R2P2CI) spectra of a series of Aniline-Ar, complexes (n --1 -6). An apparently anomalous blue shifted spectra for An-Ar 3 is explained by a modified spectral shift additivity rule which assigns different shifts to different relative positions of the Ar with respect to aniline. Evidence is presented for the existence of several isomers of clusters with n > 2. It is shown that, by changing the nucleation conditions, it is possible to control the relative populations of the various isomers.

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Intermolecular vibronic spectroscopy of small Van Der Waals clusters: phenol- and aniline-(argon)2 complexes

Abstract: We report the dear observation and assignment of the symmetric stretching and bending van der Waats modes in two three-body Czv complexes, phenol-and aniline-(Ar)2, using resonant two-photon ionization.

Cited by 30 publications

References 8 publications

The structure of phenol-Arn (n=1,2) clusters in their S and S1 states

The structure of phenol-Arn (n=1,2) clusters in their S and S1 states

IR signature of the photoionization-induced hydrophobic→hydrophilic site switching in phenol-Arn clusters

Resonant two-photon two-color photoionization (R2P2CI) spectra of aniline-Ar n clusters: Isomer strutures and solvent shifts

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