Acs Jpca 8b04446

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A: Spectroscopy, Molecular Structure, and Quantum Chemistry

Infrared Spectroscopy of Protonated Phenol-Water Clusters
Marusu Katada, and Asuka Fujii
J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.8b04446 • Publication Date (Web): 20 Jun 2018
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Page 1 of 55 The Journal of Physical Chemistry
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6 Infrared Spectroscopy of Protonated Phenol-
Phenol-Water Clusters
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9 Marusu Katada and Asuka Fujii*
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Department of Chemistry, Graduate School of Science, Tohoku University,
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14 Sendai 980-8578, Japan
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17 *Corresponding author
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19 E-mail: asukafujii@m.tohoku.ac.jp
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21 ORCID Asuka Fujii: 0000-0002-6854-9636
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26 Abstract
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29 To explore the microhydration structures of protonated phenol, size-selective infrared
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32 spectroscopy of protonated phenol-(water)n clusters (n = 1 – 5) was performed.
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35 Protonation of phenol can occur either at the phenyl ring or the hydroxy group. The
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38 coexistence of the two isomer types separated by the high isomerization barrier was
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reconfirmed for bare protonated phenol. Preferential hydration of the hydroxy group
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43 initially occurs in both the two isomer types of protonated phenol. Development of the
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46 water hydrogen-bond network is localized around the hydroxy group up to n = 2.
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49 Intracluster proton transfer from the phenol moiety to the water moiety was observed in
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52 n ≥ 3~4. The water moiety with the H3O+ ion core resides on the phenyl ring, and the
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55 water moiety is bound to the phenyl ring with a π-hydrogen bond. Such a structure is
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60 ACS Paragon Plus Environment
The Journal of Physical Chemistry Page 2 of 55
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6 in striking contrast to those of phenol+-(water)n radical cation clusters, in which the
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9 water moiety is located away from the phenyl ring even when intracluster proton
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transfer occurs.
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17 1. Introduction
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20 Protonated aromatic molecules have attracted much interest in the diverse fields of
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23 chemistry and biochemistry. 1-7 Protonated aromatics are well-known crucial
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26 intermediates in electrophilic aromatic substitution reactions. 1 The presence of
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protonated aromatics in interstellar space has been suggested. 2,3 Moreover, protonated
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31 aromatics are expected to play important roles in biochemical processes since the proton
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34 is one of the major carriers of positive charge in such systems. 4 Therefore,
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37 characterization of protonated aromatic molecules and their microsolvated clusters in
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40 the gas phase has been extensively performed by spectroscopic, mass spectrometric, and
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43 theoretical approaches. 5-45 Not only the structure determination, e.g., identification of
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the protonated site and their microsolvation structures, but also (excited state) proton
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48 transfer mechanisms have been studied.
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51 The simplest prototype of protonated aromatics is protonated benzene. 8-16
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54 Protonated benzene has the arenium (benzenium) ion structure, in which the
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57 2
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1
2
3
4
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6 protonated carbon atom has the sp3 hybridization and the resonance among the π
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9 orbitals is partly broken. This type of protonated species is also called σ-complex or
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Wheland intermediate. Though the proton affinity (PA) of benzene (750 kJ/mol) is larger
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14 than water (PA = 691 kJ/mol), 46 the hydration of protonated benzene with only a single
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17 water molecule induces the proton transfer reaction to form protonated water
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20 (hydronium ion, H3O+). 13 This is due to the large solvation energy of the hydronium
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23 ion by benzene with the strong charge-induced dipole interaction.
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26 On the other hand, in substituted benzene molecules, 19-45 the protonation of the
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substituent competes with the protonation of the phenyl ring, and the former process
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31 can be exclusive when the “local” proton affinity of the substituent is much larger than
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34 that of the phenyl ring moiety. Such a case has been found in benzaldehyde. 27-31 In
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37 this context, protonated phenol, H+PhOH, is of great interest because competition
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40 between the protonation of the substituent (hydroxy (OH) group) and the phenyl ring
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43 has been observed. 19-26 Solcà and Dopfer have applied infrared (IR) dissociation
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spectroscopy to H+PhOH. 19-21 They found that at least two isomers of H+PhOH coexist
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48 under the jet-cooled condition. In the most stable structure, the excess proton is located
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51 at the para (p-) position of the phenyl ring, resulting in an arenium ion. In the second
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54 stable structure, the excess proton is located at the ortho (o-) position of the phenyl ring.
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57 3
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6 Protonation of the meta (m-) and ipso positions is much less stable. Since the arenium
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9 ions produced by the protonation at the p- and o-positions are difficult to distinguish by
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spectroscopy, hereafter we call them both Ph-type. Solcà and Dopfer have reported
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14 that the excess proton can also be located at the lone pair electrons of the OH group and
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17 this forms an oxonium ion. Hereafter, this isomer is called O-type. Though the
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20 relative energy of the O- type is over 70 kJ/mol higher than that of the most stable
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23 Ph-type, Solcà and Dopfer have observed the competitive production of the O-type
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26 isomer under the supersonic jet expansion cooling condition, and they attributed it to
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the high potential energy barrier (~160 kJ/mol) in the isomerization from the O-type to
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31 the Ph-type.
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34 The microsolvation of H+PhOH is also of great interest. Solcà and Dopfer
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37 performed IR spectroscopic studies on the microsolvation by inert gas species (Ne, Ar,
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40 and N2). 19-21 They showed that the solvation begins with hydrogen (H-) bond formation
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43 to the acidic OH group(s) and then proceeds to π-bond formation, while intermolecular
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binding to the aliphatic CH2 group in the protonated phenyl ring is not preferred. On
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48 the other hand, studies on the microsolvation of H+PhOH by water have been very
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51 scarce in spite of its special importance in relation to the protonation of tyrosine in
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54 biological environments. H-bonded structures of H+PhOH-(water)n (H+PhOH-Wn)
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57 4
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6 clusters and the size dependence of their intracluster proton transfer have been studied
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9 by quantum chemical computations and energy-resolved collision-induced dissociation
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(CID) measurements. 24, 26 However, the computations were performed for only a small
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14 number of hydrated structures based on the Ph-type isomer. 24 It is also difficult to
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17 definitively infer H-bonded structures of clusters from CID experiments because
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20 rearrangements of clusters can occur prior to dissociation.
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23 On the other hand, neutral phenol-water clusters (PhOH-Wn) and phenol-water
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26 radical cation clusters (PhOH+-Wn) have been extensively studied in the gas phase. 47-66
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Neutral PhOH-Wn has been investigated by size-selective IR spectroscopy as a model of
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31 water H-bond networks. 47-59 It has been demonstrated that the H-bond network of
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34 PhOH-Wn develops from ring structures to cage structures as the cluster size increases.
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37 47-57 Further processes to form bulk-like structures including fully solvated water
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40 molecules have been discussed. 58,59 The H-bonded structures of PhOH+-Wn have also
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43 been investigated by IR and electronic spectroscopies, and the occurrence of intracluster
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proton transfer from the phenol cation to the water moiety has been confirmed in n ≥ 3 ~
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48 4. 60-66 We should note that both the H-bonded networks of neutral and cationic
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51 hydrated phenols develop around the phenolic OH group and a direct interaction
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54 between the water network and the phenyl ring has not yet been observed in these
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57 5
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1
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6 systems.
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9 As mentioned above, the two isomer types of H+PhOH coexist under the jet-cooled
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condition. 19-21 The differences in the microhydration structures between these two
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14 types and interconversion between the isomers with the development of hydration are of
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17 great interest. In the present study, we apply IR dissociation spectroscopy to the
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20 H+PhOH-Wn (n = 1- 5) clusters to explore the development of the H-bond network
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23 structures of these clusters with the help of quantum chemical calculations and by
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26 comparison with related systems. The IR spectrum of the H+PhOH monomer was
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measured by the Ar-tagging method to determine the isomer ratio under the
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31 experimental conditions as well as to confirm the presence or absence of radical cation
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34 species. 67-69
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37
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40 2. Experimental
Experimental and Computational Methods
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43 Size-selective IR spectra of H+PhOH-Ar and H+PhOH-W1-5 in the OH and CH stretching
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vibrational region (2800 - 3900 cm-1) were measured by IR dissociation spectroscopy.
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48 The mass selection of the clusters was performed by a tandem-type quadrupole mass
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51 spectrometer. 68, 69 Protonated clusters were generated by electron ionization with an
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54 electron gun (Omegatron Co.) followed by supersonic jet expansion cooling. The sample
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57 6
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1
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3
4
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6 of phenol (Kanto Chemical Co.) was used without further purification. Phenol was
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9 heated to ~280 K in the sample container of a high pressure supersonic jet valve
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(Even−Lavie valve). 70 The phenol vapor was seeded in the carrier gas of He/Ar/H2
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14 (80:10:10) or He/H2 (95:5) containing trace water vapor. The total stagnation pressure
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17 of the jet expansion was 60-80 atm. The electron beam accelerated at a voltage of 200 V
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20 was crossed with the jet expansion in the collisional region. The protonated cluster of
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23 interest was selected by the first quadrupole mass filter and the cluster was introduced
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26 into the octopole ion guide. The size-selected cluster was irradiated by an IR laser in the
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ion guide. A fragment ion is generated via predissociation when the IR frequency is
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31 resonant on a vibrational transition of the cluster. The second quadrupole mass filter
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34 was set to pass only the fragment ion and the IR spectrum of the cluster was measured
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37 by monitoring the intensity of the fragment ion while scanning the IR frequency. The IR
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40 light was generated by an OPO/OPA system (LaserVision), and the typical IR power was
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∼2 mJ/pulse.
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The IR spectrum of the H+PhOH monomer was measured by using the He/Ar/H2
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48 carrier gas and by the Ar-tagging method. On the other hand, the IR spectra of the
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51 H+PhOH-Wn clusters were measured by using the He /H2 carrier gas and by monitoring
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54 the water-loss channel. The dissociation of PhOH was not detected in the present
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57 7
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1
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6 measurements.
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9 In the present experiment, the protonated cluster ion intensity was not high
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12 enough to achieve a mass resolution of ∆m/z <1. Under the spectral measurement
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14 conditions, the mass resolution was ∆m/z ~2 and we could not completely separate the
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17 protonated cluster from the radical cation cluster of the same cluster size. Therefore, we
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20 compared the observed IR spectrum of H+PhOH-Ar with that of PhOH+-Ar, 71,72 and
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23 confirmed that spectral contamination by the radical cations was negligible under the
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26 present cluster source condition.
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Quantum chemical calculations were performed on the H+PhOH-Ar and
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31 H+PhOH-Wn (n = 1 – 5) clusters to evaluate their H-bonded network structures based on
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34 the observed IR spectra. As will be shown later, the interaction between the water
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37 moiety and phenyl ring (π-electrons) is the key to understanding the microhydration
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40 structures of H+PhOH-Wn. Dispersion should be important in such a type of interaction.
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43 Since MP2 level computations of the present clusters were too time-consuming for our
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computational resources, we employed the dispersion-corrected density functional
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48 theory (DFT) method. For each cluster size, energy-optimized structures were
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51 calculated at the ωB97X-D/6-311++G(d, p) level, which is expected to have a good
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54 balance between computational cost and accuracy. The relative energies of the stable
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57 8
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1
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4
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6 structures with the zero-point energy correlation were evaluated and their IR spectra
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9 were simulated under the harmonic oscillator approximation. The scaling factor was set
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to 0.932 to fit the calculated OH stretch frequency of the most stable isomer of
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14 H+PhOH-Ar (Ph-type) to the most intense band in the observed IR spectrum. The
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17 atomic charge was evaluated by Mulliken population analysis to examine the origin of
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20 the free OH shift of the water moiety. All calculations were performed by the Gaussian
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23 16 program suite. 73
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26
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3. Results and Discussion
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31 A. H+PhOH-
PhOH-Ar
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34 Figure 1(a) shows the observed IR spectrum of H+PhOH-Ar produced in the present
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37 cluster source. The band at 2863 cm-1 is attributed to the aliphatic CH stretch, 5, 7, 9-11,
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40 19-21 and this band indicates the production of the (p- and/or o-) Ph-type isomer(s), in
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43 which the protonation occurs on the phenyl ring. On the other hand, the multiple bands
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in the OH stretch region demonstrate the coexistence of the O-type isomer, which is
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48 protonated at the hydroxy group. The observed bands are the same as those previously
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51 reported by Solcà and Dopfer, 19-21 but the intensity distribution is somewhat different,
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54 reflecting the different isomer population ratio.
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57 9
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1
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4
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6 Figures 1(c)-(e) represent the IR spectral simulations based on the Ph-type (p-),
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9 Ph-type (o-), and O-type isomers, respectively. The most intense peak at 3499 cm-1 in
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the observed spectrum is assigned to the Ar-bound OH stretch of the Ph-type isomer.
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14 The Ph-type (p-) isomer is much more stable than the Ph-type (o-) isomer, but a high
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17 isomerization barrier (~90 kJ/mol) is predicted for these isomers by Solcà and Dopfer.
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20 19-21 The Ph-type (p-) and Ph-type (o-) isomers show almost identical spectra, and we
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23 cannot experimentally distinguish between them. Though the coexistence of these two
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26 isomers is not excluded, we focused only on the more stable Ph-type (p-) isomer in the
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following discussions for simplicity. The relatively broadened band at 3336 cm-1 and
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31 the second intense band at 3533 cm-1 are attributed to the Ar-bound and free OH
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34 stretches of the O-type isomer, respectively. A weak band is seen at 3554 cm-1 in the
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37 observed spectrum. Solcà and Dopfer have assigned this band to the free OH stretch of
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40 the Ph-type isomer with the π-bound Ar tag. 19-21
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43 The relative energy of the O-type is much higher (+73 kJ/mol) than the Ph-type,
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but the O-type clearly dominates. This is due to the high barrier in the isomerization
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48 process, as discussed by Solcà and Dopfer. 19-21 Figure 1(b) shows the Lorentzian fitting
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51 of the observed spectrum after slight smoothing (the upper trace shows the residual in
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54 the fitting). On the basis of the integrated band intensities estimated by the fitting
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57 10
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1
2
3
4
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6 and the calculated transition intensities, the relative population of the Ph-type (p- and
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9 o-) and O-type is evaluated as ~4:1. In this measurement, we employed the jet
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expansion of the stagnation pressure at 60 atm, whereas Solcà and Dopfer reported a
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14 ratio of ~5:1 in the jet expansion (with electron ionization) at 12 atm. 20 The higher
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17 production yield of the less stable O-type isomer under the higher pressure jet
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20 expansion condition might be due to kinetic trapping to the local minimum with the
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23 rapid cooling process.
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26 Since the mass resolution of the present experimental condition was not high
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enough (∆m/z ~2) to completely separate H+PhOH-Ar from the PhOH+-Ar radical cation,
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31 we examined its spectral contamination by comparison of the observed IR spectra. The
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34 IR spectrum of PhOH+-Ar produced by an electron ionization source is shown in Fig. 1(f),
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37 which is taken from ref. 72. It has been known that PhOH+-Ar has two stable isomers
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40 with the Ar-binding sites. The Ar-bound OH stretch band of PhOH+-Ar is seen at 3464
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43 cm-1 in the H-bonded isomer, while the band at 3536 cm-1 is attributed to the free OH
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stretch of the π-bonding isomer. 71, 72 With the electron ionization at the collisional
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48 region of the jet expansion, the more stable H-bonded isomer is the major product. 72
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51 In the present spectrum (Fig. 1(a)), the Ar-bound OH stretch band of PhOH+-Ar at 3464
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54 cm-1 is nearly absent. Therefore, we conclude that the spectral contamination by the
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57 11
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1
2
3
4
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6 radical cation species is essentially negligible in the present measurements. In our
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9 previous study of the PhOH+-Wn radical cation clusters, the ions were produced by
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resonance multiphoton ionization of the phenol moiety and low pressure jet expansion
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14 with the neat He carrier gas, and the radical cation species were dominant products. 61
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17 In the present condition, we employed electron ionization and high pressure jet
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20 expansion, and also added H2 to the carrier gas to promote the protonation. These
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23 factors would be effective to efficiently quench the radical cation species. In the
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26 following discussion, we ignore the contribution of the radical cations and focus on the
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protonated species.
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31 B. H+PhOH-
PhOH-W1
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34 Figure 2(a) shows the observed IR spectrum of H+PhOH-W1 in the OH and CH stretch
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37 region. In the spectrum, the CH stretch band of the aliphatic CH2 group appears at 2864
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39
40 cm-1, which is essentially the same frequency as that in the monomer. Moreover, a
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43 remarkably broadened absorption is seen around 2900 cm-1 and this band is attributed
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to a H-bonded OH stretch. These spectral features suggest a cluster structure in which
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48 the Ph-type isomer is solvated at the OH group by a water molecule. The simulated IR
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51 spectrum and schematic structure of the minimum energy structure is shown in Fig.
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54 2(c). The phenolic OH group of the Ph-type isomer acts as a proton donor to the water
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57 12
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1
2
3
4
5
6 moiety. This structure is essentially the same as that proposed in the previous CID and
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9 theoretical studies, 24, 26 and its simulated spectrum well reproduces the observed
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11
spectrum in the region below 3500 cm-1. However, the observed spectrum shows three
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13
14 free OH stretch bands at 3585, 3626, and 3713 cm-1. While the latter two bands can be
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17 assigned to the symmetric and antisymmetric (ν1 and ν3) stretching vibrations of the
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20 water moiety, the former band at 3585 cm-1 cannot be attributed to the most stable
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23 Ph-type isomer. Therefore, this band indicates the coexistence of the O-type isomer
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26 shown in Fig. 2(d), in which the O-type monomer is hydrated at the protonated phenolic
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hydroxy group. Its free phenolic OH would be the spectral carrier of the 3585 cm-1
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31 band (the H-bonded phenolic OH stretch band is calculated below 2600 cm-1). The
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34 relative energy of the O-type isomer is much higher (+43.1 kJ/mol) than the most stable
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37 Ph-type isomer. However, this large energy difference essentially comes from that
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39
40 between the monomer isomers (here, we should note that the energy difference in the
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43 hydrated clusters is significantly reduced, indicating a stronger interaction with water
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in the O-type isomer). The coexistence of the monomer isomers by the high potential
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48 barrier rationalizes the coexistence of the hydrated isomers. We estimated the
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51 population ratio of the Ph- and O-type isomers based on the band area evaluation by
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54 Lorentzian fitting (Fig. 2(b)) and the computed vibrational transition intensities. As a
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57 13
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59
1
2
3
4
5
6 result, we evaluated the ratio between the Ph- and O-types to be ~4:1. This ratio is the
7
8
9 same as that estimated for the isomers of H+PhOH-Ar, and suggests that the high
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11
isomerization barrier between the Ph-type and O-type is still present in H+PhOH-W1.
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14 The binding of the water molecule to the protonated CH2 moiety in the phenyl
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17 ring also forms a few stable structures. In such a structure, the water molecule becomes
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20 a single acceptor and therefore such a structure can be called CH-O type. The most
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23 stable structure among this type of isomer and its IR spectral simulation are shown in
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26 Fig. 2(e). This isomer is, however, much higher in energy (+38.4 kJ/mol) than the most
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stable Ph-type isomer. In the CH-O type isomer, the strong H-bonded aliphatic CH
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31 stretch band is predicted at ~2600 cm-1 (the lower frequency side of the free aliphatic
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34 CH stretch). However, the observed broadened absorption is well represented by a
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36
37 single peak centered at ~2900 cm-1. Moreover, the free phenolic OH stretch frequency
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40 of the CH-O type isomer is reasonably expected to be very close to that in π-bound
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42
43 H+PhOH-Ar (Ph-type), which is 3554 cm-1 in the observed spectrum (see Fig. 1(a)).
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45
However, such a band is missing in the observed spectrum. Therefore, we conclude
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48 that the production of this type of isomer is negligible. This is also consistent with the
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51 results of the microsolvation of H+PhOH by inert gas species; the solvation of the OH
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53
54 group is far superior to that of the CH2 group. 19-21 The absence of the CH-O type
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57 14
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59
1
2
3
4
5
6 isomer indicates that the barrier to the water transfer is lower than that of the proton
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8
9 transfer.
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11
In the observed spectrum, weak bands are seen above 3750 cm-1. The
12
13
14 frequencies of these bands are too high to be fundamental vibrations. Therefore, these
15
16
17 bands are attributed to combination bands of the water free OH bands and
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19
20 intermolecular vibrations.
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22
23 The observed H-bonded structures of H+PhOH-W1 are similar to those reported
24
25
26 for neutral PhOH-W1 and PhOH+-W1. 48, 49, 51, 55, 61-65 In these clusters, the water
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28
molecule acts as a proton acceptor to the phenolic OH. The ν1 and ν3 frequencies of the
29
30
31 water moiety are 3650 and 3748 cm-1 in neutral PhOH-W1, 48 while they are 3626 and
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34 3709 cm-1 in PhOH+-W1, respectively. 64 The small red-shifts of the bands in PhOH+-W1
35
36
37 are attributed to the influence of the excess charge, which also clearly enhances the
38
39
40 intensity of the ν1 band, whose transition dipole moment is parallel to the electric field
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42
43 of the excess charge. The ν1 and ν3 frequencies of H+PhOH-W1 (Ph-type) are 3626 and
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45
3713 cm-1, respectively, and they are very close to those of PhOH+-W1. The charge
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47
48 distribution of H+PhOH estimated by the Mulliken population analysis is discussed in
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51 the Supporting Information (SI). The Mulliken charge (0.264) of the OH group of
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53
54 H+PhOH (Ph-type) is much closer to that of PhOH+ radical cation (0.29) than neutral
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57 15
58
59
1
2
3
4
5
6 PhOH (0.038). This charge evaluation is consistent with the trend of the observed
7
8
9 frequency shifts of the water free OH bands.
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11
C. H+PhOH-
PhOH-W2
12
13
14 The observed IR spectrum and spectral simulations of H+PhOH-W2 are shown in Fig. 3.
15
16
17 The very intense and broadened H-bonded OH band seems to disappear from the
18
19
20 observed region at this cluster size. Instead, a moderately intense H-bonded OH band is
21
22
23 seen at ~3240 cm-1. This band indicates the presence of a H-bond between neutral
24
25
26 molecules. Three free OH stretch bands also appear in the high frequency region. The
27
28
bands at 3638 and 3725 cm-1 are assigned to the ν1 and ν3 bands of a single acceptor
29
30
31 water molecule, respectively, and the band at 3685 cm-1 is from a dangling OH of an
32
33
34 acceptor-donor (two-coordinated) water molecule. These band features suggest a
35
36
37 linear-chain type H-bonded structure with a Ph-type core as shown in the inset of Fig.
38
39
40 3(c). Its simulation well reproduces the observed spectral features, indicating that this
41
42
43 is the major isomer of H+PhOH-W2. This structure has been predicted in the previous
44
45
theoretical study by Ataelahi and Omidyan. 24 In the present simulation, an intense
46
47
48 H-bonded OH stretching band is predicted at around 2600 cm-1, but this band is missing
49
50
51 in the observed spectrum. This band is due to the strongly H-bonded phenolic OH
52
53
54
55
56
57 16
58
59
1
2
3
4
5
6 stretch, and the present harmonic approximation would result in a large overestimation
7
8
9 of the vibrational frequency.
10
11
A CH---O type isomer is also stable in this size. However, its energy is much
12
13
14 higher (+25 kJ/mol) than the most stable Ph-type isomer shown in Fig. 3(c). The absence
15
16
17 of the free phenolic OH stretching band at around 3550 cm-1 supports the negligible
18
19
20 population of this type of isomer.
21
22
23 In neutral PhOH-W2, the H-bonded network forms a cyclic structure while the
24
25
26 chain type structure is preferred in PhOH+-W2. 48-51,53,-55, 56, 57, 61, 62, 65 This structural
27
28
difference can be attributed to the enhanced acidity of the phenolic OH in the cation,
29
30
31 which results in a preference for the straight OH---O H-bond angle. The reduced
32
33
34 basicity of the phenolic OH in the cation also prohibits it from accepting a proton to
35
36
37 form a cyclic structure. The observed structure of H+PhOH-W2 is similar to that of
38
39
40 PhOH+-W2, and this reflects the similar charge distribution in the OH groups in PhOH+
41
42
43 and H+PhOH.
44
45
The band width of the ν1 and ν3 bands of the observed spectrum of H+PhOH-W2
46
47
48 seems larger than that of the dangling OH band. This suggests overlap of bands due to
49
50
51 coexistence of a minor isomer. The structure and simulated IR spectrum of the most
52
53
54 stable isomer with the O-type protonated core are shown in Fig. 3(d). In this structure,
55
56
57 17
58
59
1
2
3
4
5
6 both the water molecules are directly bound to the protonated site (OH2+ group), and
7
8
9 their ν1 and ν3 bands are shifted to lower frequency by ~20 cm-1 in comparison with
10
11
those of the Ph-type isomer. The overlap of these bands well explains the larger
12
13
14 bandwidth of the observed spectrum. The relative population ratio between the
15
16
17 Ph-type and O-type isomers is roughly estimated to be ~7:1 based on the band fitting
18
19
20 shown in Fig. 3(b) and the computational transition intensities. Though the energy
21
22
23 difference between the Ph-type and O-type isomers becomes smaller with the progress
24
25
26 of the hydration, they are still separated by the high isomerization barrier. The smaller
27
28
relative population of the O-type isomer at this size may reflect the small population of
29
30
31 its precursor, H+PhOH-W0-1.
32
33
34 D. H+PhOH-
PhOH-W3
35
36
37 Figure 4(a) shows the observed IR spectrum of H+PhOH-W3 measured by monitoring
38
39
40 the water-loss channel. No signal was detected by monitoring the PhOH-loss channel.
41
42
43 H-bonded OH stretch bands are seen at ~3200 and ~3400 cm-1, and two free OH
44
45
stretching bands assigned to the ν1 and ν3 bands of single acceptor water appear at 3646
46
47
48 and 3733 cm-1, respectively. On the other hand, the dangling OH band, which is
49
50
51 intense in the spectrum of H+PhOH-W2, is remarkably suppressed. A weak band at
52
53
54 ~3800 cm-1 is attributed to a combination band of free OH stretch and intermolecular
55
56
57 18
58
59
1
2
3
4
5
6 vibration. These features clearly indicate that the H-bonded water network is no longer
7
8
9 a simple linear chain type, and terminal water molecules in the network should be
10
11
single acceptors. Multiple interpretations are possible for the observed spectrum, and
12
13
14 we examine each interpretation in the following discussion.
15
16
17 The Ph-type structure shown in Fig. 4(c) is reasonably derived from the major
18
19
20 isomer of H+PhOH-W2. This structure satisfies the above-mentioned requirements
21
22
23 and its IR simulation qualitatively reproduces the observed spectral pattern. The
24
25
26 observed H-bonded OH stretch bands at ~3200 and ~3400 cm-1 are attributed to the
27
28
symmetric and antisymmetric OH stretches, respectively, of the water molecule directly
29
30
31 bound to the phenolic OH group. The symmetric OH stretch of such a water molecule
32
33
34 bound to the charged site frequently shows a larger intensity enhancement than the
35
36
37 antisymmetric OH stretch. 74 This trend agrees well with the observed intensity
38
39
40 distribution. However, the simulation fails to reproduce the observed intensity
41
42
43 distribution. The structure of this Ph-type isomer is similar to that of PhOH+-W3 but
44
45
largely different from neutral PhOH-W3 which has a cyclic structure. 48,49,51,53,55,61,62,64
46
47
48 We searched stable isomers of H+PhOH-W3, and found that the proton transferred
49
50
51 structure shown in Fig.4(d) is the most stable isomer at the ωB97X-D/6-311++G(d, p)
52
53
54 level. This isomer is derived from an initial O-type isomer with the proton transfer
55
56
57 19
58
59
1
2
3
4
5
6 from the PhOH moiety to the water moiety. The previous theoretical study on
7
8
9 H+PhOH-Wn by Ataelahi and Omidyan lacked the proton-transferred structure at this
10
11
size since their main focus was on the excited electronic state dynamics and their initial
12
13
14 structures in the energy optimization were limited to those with the Cs symmetry. 24
15
16
17 Though this isomer is more stable than the Ph-type isomer (Fig. 4(c), +13.9 kJ/mol), the
18
19
20 band fitting shown in Fig. 4(b) demonstrates that its contribution might be minor. The
21
22
23 isomer shown in Fig. 4(e) is another proton-transferred isomer also derived from the
24
25
26 O-type isomer. Though this isomer is higher in energy (+8.6 kJ/mol), its band at 3400
27
28
cm-1 (the water OH stretch bound to the phenyl oxygen) agrees well with the observed
29
30
31 band, and its partial contribution seems plausible.
32
33
34 In the previous study on the protonated benzene water clusters, Duncan and
35
36
37 coworkers demonstrated that DFT methods (including dispersion-corrected ones) have
38
39
40 trouble in evaluating the relative energy between the proton-transferred and
41
42
43 non-proton transferred species. 13 Because of the similarity between the systems, we
44
45
cannot exclude the possibility of large errors in the present energy evaluation. Moreover,
46
47
48 in H+PhOH-Wn, the isomer population does not necessarily reflect the relative energy
49
50
51 because of the potential barrier, as clearly demonstrated in the monomer. Duncan and
52
53
54 coworkers showed that comparison with the spectra of protonated water is helpful to
55
56
57 20
58
59
1
2
3
4
5
6 identify the proton-transferred structure when the energy evaluation is useless. 13, 75
7
8
9 Thus, the IR spectrum of H+(H2O)3-benzene is compared with the present IR spectrum
10
11
of H+PhOH-W3. Fig. 4(f) is the reproduction of the IR spectrum of H+(H2O)3-benzene
12
13
14 taken from ref. 13. In this cluster, the excess proton is in the water moiety, and the
15
16
17 resulting hydronium ion (H3O+) is π-H-bonded to the phenyl ring. The π-H-bonded OH
18
19
20 stretch band of the hydronium ion appears at 3192 cm-1. The spectrum of
21
22
23 H+(H2O)3-benzene is quite similar to that of H+PhOH-W3, and this suggests the proton
24
25
26 transfer from phenol to the water moiety occurs at this size. However, the 3400 cm-1
27
28
band of H+PhOH-W3 is absent in the spectrum of H+(H2O)3-benzene. If this band is
29
30
31 attributed to the water OH stretch bound to the phenyl oxygen, as seen in the isomer of
32
33
34 Fig. 4(e), one of the neutral water molecules becomes a donor-acceptor (two-coordinated)
35
36
37 site, and its free OH should show the dangling OH band at ~3700 cm-1. However, as
38
39
40 seen in the band fitting in Fig. 4(b), such a band should be very weak. Therefore, any
41
42
43 single isomer cannot explain all the spectral features. Since the Ph- and O-types
44
45
coexist in H+PhOH-Wn<3, which might be precursors in the H+PhOH-W3 production, the
46
47
48 coexistence of both the non-proton-transferred isomers (the Ph-type) and
49
50
51 proton-transferred isomer (from the O-type) also seems highly plausible in H+PhOH-W3.
52
53
54
55
56
57 21
58
59
1
2
3
4
5
6 At the present stage, unequivocal determination of the isomer structure of H+PhOH-W3
7
8
9 is difficult.
10
11
E. H+PhOH-
PhOH-W4
12
13
14 The observed IR spectrum of H+PhOH-W4 is shown in Fig. 5(a). The number of band
15
16
17 features suddenly increases, and the spectrum is much more complicated. This suggests
18
19
20 a large change in the H-bonded network structure (of the major isomer) at this size. A
21
22
23 characteristic feature of the spectrum is the band at 3540 cm-1. This is the region where
24
25
26 the free phenolic OH stretch of H+PhOH (Ph-type) is expected. 19-21 However, the
27
28
phenolic OH is preferentially H-bonded by water, and the free phenolic OH band is not
29
30
31 actually seen in the spectra of H+PhOH-Wn (n = 1- 3). Therefore, this band is
32
33
34 attributed to a weakly H-bonded OH stretch of the neutral water moiety. 76 The most
35
36
37 stable isomer we found at this size is shown in Fig. 5(b). This isomer has a proton
38
39
40 transferred structure with the H3O+ ion core, and a neutral water moiety is bound to the
41
42
43 phenyl ring by a π-H-bond. Its simulated spectrum well reproduces the observed
44
45
spectral features above 3400 cm-1, and the observed band at 3540 cm-1 is assigned to the
46
47
48 π-H-bonded OH stretch (here, we should note that if the H3O+ moiety is directly bound
49
50
51 to the phenyl ring, its π-H-bonded OH is shifted to much lower frequency (~3200 cm-1),
52
53
54 13 as seen in the spectrum of H+(H2O)3-benzene in Fig. 4(f)). However, the agreement in
55
56
57 22
58
59
1
2
3
4
5
6 the low frequency region is only qualitative. This can be partly attributed to the large
7
8
9 influence of anharmonicity and significant line broadening expected for the H-bonded
10
11
OH bands lower than ~3000 cm-1. However, contributions of other isomers are also
12
13
14 suggested. Some low energy isomers that also have the protonated water core (H3O+)
15
16
17 and π-H-bond are found (Figs. 5(c)-(d)), and the observed features might be partially
18
19
20 attributed to these coexisting isomers.
21
22
23 In the n = 1 – 3 clusters, preferential hydration of the phenolic OH group is
24
25
26 seen, and the water moiety is rather isolated from the protonated CH2 site in the major
27
28
Ph-type. Therefore, as discussed for n = 3, the proton transfer might occur only in the
29
30
31 minor O-type. At the present size (n = 4), the water network can be long enough to link
32
33
34 the phenyl ring to the phenolic OH group. Therefore, proton transfer can occur from
35
36
37 both the Ph- and O-types, and this results in the dominance of the proton transferred
38
39
40 structures. When the water moiety is still separated from the CH2 site, the proton
41
42
43 transfer from the phenolic OH can occur but the resulting structure is estimated to be
44
45
much higher in energy (+32.9 kJ/mol) as shown in Fig. 5(e).
46
47
48 It is very interesting that the protonated water moiety prefers to be bound to
49
50
51 the phenyl ring through the π-H-bond. In PhOH+-Wn, though the proton transfer from
52
53
54 PhOH+ to the water moiety also occurs at n = 3 or 4, the water H-bond network is
55
56
57 23
58
59
1
2
3
4
5
6 extended in front of the phenoxy oxygen atom, and the π-H-bond formation has never
7
8
9 been observed. 60-62, 64, 66 Once the proton is transferred to the water moiety, neutral
10
11
phenol is formed in H+PhOH-Wn, while phenoxy radical is formed in PhOH+-Wn. The
12
13
14 hydroxy oxygen in neutral phenol has sp3 hybridization, and the H-bond to the phenolic
15
16
17 oxygen directs the water moiety out of the plane of the phenyl ring (see Figs. 5(b)-(d)).
18
19
20 This location of the water moiety gives it good accessibility to the phenyl ring plane to
21
22
23 form the π-H-bond. On the other hand, the oxygen atom in the phenoxy radical can be
24
25
26 regarded as that of a carbonyl group and has sp2 hybridization. Therefore, the water
27
28
moiety H-bonded to the oxygen atom resides in the plane of the phenyl ring (see Fig.
29
30
31 5(e) for a similar case of a H-bond to a carbonyl oxygen). In this case, the accessibility
32
33
34 to the phenyl ring plane is much worse. This may prohibit the formation of a
35
36
37 π-H-bonded structure in PhOH+-Wn.
38
39
40 F. H+PhOH-
PhOH-W5
41
42
43 Figure 6 shows (a) observed IR spectrum and (b)-(d) low energy stable isomer structures
44
45
of H+PhOH-W5 and their simulated IR spectra. Since the parent ion intensity of this
46
47
48 cluster size is quite weak, the quality of the observed spectrum is worse than the other
49
50
51 sizes. The spectral features are similar to that of H+PhOH-W4. The π-H-bonded OH
52
53
54 stretch band is still seen at around 3550 cm-1, and a broad absorption of H-bonded OH
55
56
57 24
58
59
1
2
3
4
5
6 stretches appears below 3450 cm-1. In the free OH stretch region, the dangling OH
7
8
9 stretch band of an acceptor-donor (two-coordinated) water site is clearly seen at 3708
10
11
12 cm-1. The ν1 band of single acceptor water also appears at 3641 cm-1, and the ν3 band
13
14 becomes a shoulder of the dangling OH band.
15
16
17 The calculated low energy stable isomers have the proton transferred
18
19
20 structures with the H3O+ ion core, and the water network is located on the phenyl ring.
21
22
23 The observed spectral features, especially the π-H-bonded OH band at ~3550 cm-1, are
24
25
26 consistent with these structures of the low energy isomers. Similar to the case of the n =
27
28
4 cluster, such structures are strikingly different from those of PhOH+-W5, in which the
29
30
31 proton is transferred to the water moiety but the water network develops away from the
32
33
34 phenyl ring. 66 The difference in the H-bond coordination property of the O atom in the
35
36
37 aromatic moiety would be the origin of the structure difference. In H+PhOH-W5, the
38
39
40 energy separation among the isomers is very small, and the simulated IR spectra of the
41
42
43 isomers are more or less similar to each other. Therefore, definitive determination of
44
45
the structure of the observed cluster is difficult.
46
47
48 G. Ar-
Ar-tagged clusters of H+PhOH-
PhOH-Wn
49
50
51 The IR spectra of Ar-tagged clusters of H+PhOH-Wn (n = 1 -4) were also measured by
52
53
54 monitoring the Ar-loss channel. The observed spectra are summarized in Figs. S2-S5
55
56
57 25
58
59
1
2
3
4
5
6 with the comparison of the observed spectra of the corresponding bare clusters and
7
8
9 simulations. Ar-tagging is a highly useful technique to select low energy isomers and
10
11
simplify spectra of ionic clusters. 67-69 However, in the present system, the low energy
12
13
14 isomer selection by the Ar-tagging is not effective for the multiple isomers separated by
15
16
17 the high energy barrier. We found that in the size range of n = 1 - 4, the observed band
18
19
20 features of the Ar-tagged clusters were essentially the same as those of the bare clusters,
21
22
23 and no clear difference in the isomer distribution occurred by the tagging. In addition,
24
25
26 so many possible Ar-binding sites exist in these clusters, and the coexistence of multiple
27
28
isomers (due to both the bare cluster structures and the Ar-binding sites) makes the
29
30
31 observed spectra even more complex, especially in the free OH stretch region.
32
33
34 Therefore, essentially no new information was obtained from the measurement of the
35
36
37 Ar-tagged spectra.
38
39
40 4. Concluding remarks
remarks
41
42
43 The hydrogen bond structures of H+PhOH-Wn (n = 1 - 5) were studied by IR
44
45
spectroscopy in the OH and CH stretch region. The protonation of phenol occurs on the
46
47
48 phenyl ring (Ph-type) and hydroxy group (O-type), as previously reported. 19-21 The
49
50
51 coexistence of both isomer types even under the high pressure supersonic jet expansion
52
53
54 condition was reconfirmed by IR spectroscopy of H+PhOH-Ar. In both the isomer types,
55
56
57 26
58
59
1
2
3
4
5
6 the initial hydration preferentially occurs at the hydroxy group, and the water cluster
7
8
9 develops exclusively around the hydroxy group up to n = 2. These observed hydrated
10
11
structures are similar to those of the PhOH+-Wn radical cation clusters of the
12
13
14 corresponding size. The proton transferred structure with the H3O+ ion core was
15
16
17 estimated to be the most stable isomer at n = 3, but the coexistence of the
18
19
20 proton-transferred and non-proton-transferred isomers was suggested at this size.
21
22
23 The former comes from the O-type while the latter corresponds to the Ph-type. The
24
25
26 geometrical separation of the protonated CH2 site and the water moiety around the
27
28
hydroxy group prevents the proton transfer in the Ph-type isomer at this size. At n ≥ 4,
29
30
31 the proton-transferred structures become dominant. The water moiety is bound to the
32
33
34 phenyl ring by a π-H-bond, and resides in the ring plane. These structures are in
35
36
37 striking contrast to those of PhOH+-Wn (n ≥ 4), in which the proton transferred water
38
39
40 moiety is located away from the phenyl ring plane. This structural difference is
41
42
43 interpreted in terms of the difference of the hydrogen bond coordination properties of
44
45
the O atom in neutral phenol and phenoxy radical.
46
47
48 Because of the presence of the high energy barrier among multiple isomers, the
49
50
51 minimum energy isomer is not necessarily the dominantly observed isomer in
52
53
54 H+PhOH-Wn. In addition, the problem of the accuracy of DFT computations on a similar
55
56
57 27
58
59
1
2
3
4
5
6 protonated system has been pointed out. 13 Therefore, spectroscopic observations are
7
8
9 highly important to elucidate the actual microhydration process in H+PhOH-Wn.
10
11
Though we have focused on the OH stretching vibrational region in the present study,
12
13
14 observation of the fingerprint region is promising to obtain more structural information.
15
16
17 It has been reported that the protonation of benzene causes strong IR activity in carbon
18
19
20 ring distortion modes and CH bends.7, 11 Similar behaviors are expected for phenol,
21
22
23 and observation of the fingerprint region will be an important future task for further
24
25
26 unequivocal isomer structure determination. Strongly H-bonded OH stretches of the
27
28
charged site are also expected to appear below 2500 cm-1, and their observation is highly
29
30
31 important to unequivocally identify proton transfer in the clusters.
32
33
34
35
36
37 Supporting Information
38
39
40 Definitions of numbering of atoms in protonated phenol, phenol cation, and neutral
41
42
43 phenol. Charge distribution of protonated phenol, phenol cation, and neutral phenol.
44
45
Infrared spectra of protonated phenol-(water)n-Ar clusters (n = 1 -4). Complete author
46
47
48 list of ref.73.
49
50
51
52
53
54 Acknowledgements
55
56
57 28
58
59
1
2
3
4
5
6 We would like to acknowledge Dr. Toshihiko Maeyama and Dr. Yoshiyuki Matsuda for
7
8
9 their helpful discussions. This study was partly supported by a Grant-in-Aid for
10
11
Scientific Research (Project No. 18H01931) from JSPS.
12
13
14
15
16
17 Notes
18
19
20 The authors declare no competing financial interest.
21
22
23
24
25
26 References
27
28
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43 Figure 1 (a) Observed IR spectrum of H+PhOH-Ar. (b) Lorentzian fitting of the
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45 observed spectrum after slight smoothing. The upper trace is the residual in the
46 fitting. (c)-(e) Simulated IR spectra of the Ph-type (p-), Ph-type (o-), and O-type isomers
47
of H+PhOH-Ar, respectively. All the simulations were performed at the
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49 ωB97X-D/6-311++G(d, p) level and a scaling factor of 0.932 was applied to the
50 vibrational frequencies. Relative energies of the isomers are shown in kJ/mol. (f) IR
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52 spectrum of PhOH+-Ar. Reprinted with permission from ref. 72. Copyright 2000
53 Elsevier.
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45 fitting. (c)-(e) Simulated IR spectra of the Ph-type (p-), O-type, and CH-O-type isomers
46 of H+PhOH-W1, respectively. Relative energies of the isomers are shown in kJ/mol.
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fitting. (c)-(d) Simulated IR spectra of the Ph-type and O-type isomers of H+PhOH-W2,
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observed spectrum after slight smoothing. The upper trace is the residual in the
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49 fitting. (c)-(e) Simulated IR spectra of stable isomers of H+PhOH-W3. Relative energies
50 of the isomers are shown in kJ/mol. (f) IR spectrum of H+(H2O)3-benzene. Reprinted
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Figure 5 (a) Observed IR spectrum of H+PhOH-W4. (b)-(e) Simulated IR spectra of
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low energy stable isomers of H+PhOH-W5. Relative energies of the isomers are shown
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Figure for Table of Contents
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A: Spectroscopy, Molecular Structure, and Quantum Chemistry

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

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