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

Kalkman, Ivo; Brand, Christian; Vu, Thi Bao Chau; Meerts, W. Leo; Svartsov, Yuriy N.; Dopfer, Otto; Tong, Xin; Müller‐Dethlefs, Klaus; Schmitt, Michaël

doi:10.1063/1.3149780

Cited by 38 publications

(76 citation statements)

References 61 publications

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“…transitions assigned to intermolecular modes. 1,2,4 The clear and background-free appearance of the origin band ensures the clean selection of the 1 : 1 cluster without any fragmentation from higher 1 : n clusters under the employed experimental conditions. This result is also confirmed by the TOF mass spectrum recorded under the same conditions by setting UV exc resonant to the S 1 origin, which does not exhibit any PhOH-Ar n with n 4 1 (see Fig.…”

Section: Methodsmentioning

confidence: 95%

“…Especially for the smaller Ar clusters with n = 1 and 2, rotationally resolved UV spectra have provided detailed intermolecular structural parameters. 4 In the cationic ground states (D 0 ), additional induction effects of the positive charge make the OH group the most stable interaction site. This interaction switching was derived from IR spectra of ionized clusters, PhOH + -Rg, generated by aggregation of Rg atoms following ionization of PhOH, which leads predominantly to the formation of the most stable isomer.…”

Section: Introductionmentioning

confidence: 99%

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Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol–Ar cluster near the ionization threshold

Miyazaki

Yoshikawa

Michels

et al. 2015

Phys. Chem. Chem. Phys.

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The structure of the phenol-argon cluster (PhOH-Ar) in high-n Rydberg states is investigated by the newly developed technique of mass analyzed threshold ionization detected infrared (MATI-IR) spectroscopy. This method selectively measures IR spectra of molecular clusters in very high-n Rydberg states (n 4 100) utilized in zero kinetic energy (ZEKE) photoelectron and MATI spectroscopy, whose ionic cores are essentially the same as the corresponding bare cation. The MATI-IR spectrum exhibits only the free OH stretching vibration (n p OH ) when the p-bound cluster of the neutral ground electronic state (S 0 ) is resonantly excited via the S 1 origin to Rydberg states converging to its adiabatic ionization energy level, IE 0 (p). When Rydberg states converging to vibrationally excited levels of the local p-bound minimum are prepared, in addition to n p OH also the hydrogen-bonded OH stretching vibration (n H OH ) of the H-bonded global minimum is observed in the MATI-IR spectra, even for vibrational excitation of only 14 cm À1 above IE 0 (p). These results show that the p -H site switching reaction of the Ar ligand from the aromatic ring to the OH group proceeds only from vibrationally excited states in the p-bound cation core with a small barrier of less than 14 cm À1 from IE 0 (p). On the other hand, directly photoionized PhOH + -Ar shows both n H OH and n p OH in the IR spectra, even when it is just ionized to IE 0 (p). This result implies that the ionizationinduced p -H site switching occurs without excess energy in the H-bound or p-bound cations, in contrast to very high-n Rydberg states converging to levels of the p-bound cation. The different efficiencies of the site switching for the Rydberg ion core and the bare ion and the mechanism for the p -H site switching are interpreted by direct ionization from the p-bound to the H-bound structures in addition to the conventional vertical ionization and transitions to high-n Rydberg states.

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Section: Methodsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol–Ar cluster near the ionization threshold

Miyazaki

Yoshikawa

Michels

et al. 2015

Phys. Chem. Chem. Phys.

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“…2 This journal is c the Owner Societies 2011 by a single isomer with an S 1 origin at DS 1 = À69 cm À1 , 31 which was later firmly identified as the (11) isomer by rotationally-resolved LIF spectroscopy. 29 The total binding energy of (11) for loss of both Ar ligands, extracted from its MATI spectrum as B775 cm…”

Section: Introductionmentioning

confidence: 99%

“…A large number of spectroscopic 3,7,[26][27][28][29][30][31][32][33] and advanced quantum chemical studies 29,[34][35][36] demonstrate that neutral PhOH-Ar has a p-bonded (10) equilibrium structure in S 0 . Fig.…”

Section: Introductionmentioning

confidence: 99%

Structures and IR/UV spectra of neutral and ionic phenol–Arn cluster isomers (n≤ 4): competition between hydrogen bonding and stacking

Schmies

Patzer

Fujii

et al. 2011

Phys. Chem. Chem. Phys.

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The structures, binding energies, and vibrational and electronic spectra of various isomers of neutral and ionic phenol-Ar n clusters with n r 4, PhOH (+) -Ar n , are characterized by quantum chemical calculations. The properties in the neutral and ionic ground electronic states (S 0 , D 0 ) are determined at the M06-2X/aug-cc-pVTZ level, whereas the S 1 excited state of the neutral species is investigated at the CC2/aug-cc-pVDZ level. The Ar complexation shifts calculated for the S 1 origin and the adiabatic ionisation potential, DS 1 and DIP, sensitively depend on the Ar positions and thus the sequence of filling the first Ar solvation shell. The calculated shifts confirm empirical additivity rules for DS 1 established recently from experimental spectra and enable thus a firm assignment of various S 1 origins to their respective isomers. A similar additivity model is newly developed for DIP using the M06-2X data. The isomer assignment is further confirmed by Franck-Condon simulations of the intermolecular vibrational structure of the S 1 ' S 0 transitions. In neutral PhOH-Ar n , dispersion dominates the attraction and p-bonding is more stable than H-bonding. The solvation sequence of the most stable isomers is derived as (10), (11), (30), and (31) for n r 4, where (km) denotes isomers with k and m Ar ligands binding above and below the aromatic plane, respectively. The p interaction is somewhat stronger in the S 1 state due to enhanced dispersion forces. Similarly, the H-bond strength increases in S 1 due to the enhanced acidity of the OH proton. In the PhOH + -Ar n cations, H-bonds are significantly stronger than p-bonds due to additional induction forces. Consequently, one favourable solvation sequence is derived as (H00), (H10), (H20), and (H30) for n r 4, where (Hkm) denotes isomers with one H-bound ligand and k and m p-bonded Ar ligands above and below the aromatic plane, respectively. Another low-energy solvation motif for n = 2 is denoted (11) H and involves nonlinear bifurcated H-bonding to both equivalent Ar atoms in a C 2v structure in which the OH group points toward the midpoint of an Ar 2 dimer in a T-shaped fashion. This dimer core can also be further solvated by p-bonded ligands leading to the solvation sequence (H00),

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“…Phenol-Ar 2 provides a recent example where the S 1 vibrational structure of an aromatic-Rg 2 trimer has been observed. 22,23 The formulae provided by Bieske et al allow the six FBAr 2 (1|1) intermolecular vibrational frequencies to be calculated from the three FB-Ar intermolecular frequencies and various constants associated with the complex. 15 (The six FBAr 2 (1|1) intermolecular modes are the symmetric and asymmetric motions associated with the long axis bend, short axis bend, and the stretch -see Table IV.)…”

Section: B the Fb-ar 2 (1|1) Van Der Waals Vibrationsmentioning

confidence: 99%

Intermolecular vibrations of fluorobenzene-Ar up to 130 cm−1 in the ground electronic state

Gascooke¹,

Alexander²,

Lawrance³

2012

The Journal of Chemical Physics

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Sixteen intermolecular vibrational levels of the S 0 state of the fluorobenzene-Ar van der Waals complex have been observed using dispersed fluorescence. The levels range up to ∼130 cm −1 in vibrational energy. The vibrational energies have been modelled using a complete set of harmonic and quartic anharmonic constants and a cubic anharmonic coupling between the stretch and long axis bend overtone that becomes near ubiquitous at higher energies. The constants predict the observed band positions with a root mean square deviation of 0.04 cm −1 . The set of vibrational levels predicted by the constants, which includes unobserved bands, has been compared with the predictions of ab initio calculations, which include all vibrational levels up to 70-75 cm −1 . There are small differences in energy, particularly above 60 cm −1 , however, the main differences are in the assignments and are largely due to the limitations of assigning the ab initio wavefunctions to a simple stretch, bend, or combination when the states are mixed by the cubic anharmonic coupling. The availability of these experimental data presents an opportunity to extend ab initio calculations to higher vibrational energies to provide an assessment of the accuracy of the calculated potential surface away from the minimum. The intermolecular modes of the fluorobenzene-Ar 2 trimer complex have also been investigated by dispersed fluorescence. The dominant structure is a pair of bands with a ∼35 cm −1 displacement from the origin band. Based on the set of vibrational modes calculated from the fluorobenzene-Ar frequencies, they are assigned to a Fermi resonance between the symmetric stretch and symmetric short axis bend overtone. The analysis of this resonance provides a measurement of the coupling strength between the stretch and short axis bend overtone in the dimer, an interaction that is not directly observed. The coupling matrix elements determined for the fluorobenzeneAr stretch-long axis bend overtone and stretch-short axis bend overtone couplings are remarkably similar (3.8 cm −1 cf. 3.2 cm −1 ). Several weak features seen in the fluorobenzene-Ar 2 spectrum have also been assigned.

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

Cited by 38 publications

References 61 publications

Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol–Ar cluster near the ionization threshold

Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol–Ar cluster near the ionization threshold

Structures and IR/UV spectra of neutral and ionic phenol–Arn cluster isomers (n≤ 4): competition between hydrogen bonding and stacking

Intermolecular vibrations of fluorobenzene-Ar up to 130 cm−1 in the ground electronic state

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