Photodissociation Dynamics of 4-Aminobenzonitrile<sup>+</sup>(Water)<sub>n</sub>Clusters

Lee, Mi-Ae; Nam, Sang-Hwan; Park, Hye-Sun; Cheong, Nu-Ri; Ryu, Soojung; Song, Jae Kyu; Park, Seung Min

doi:10.5012/bkcs.2008.29.11.2109

Cited by 7 publications

(3 citation statements)

References 22 publications

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“…The barrier between the two equivalent NH-bound global minima at the transition state with C 2v symmetry is rather large (1237 cm -1 ), preventing facile interconversion by thermal excitation or tunneling. Previous calculations for the binding energy of the NH isomer at the B3LYP/cc-pVDZ level 19 yield D 0 = 6876 cm −1 , which drastically overestimates the H-bond interaction and leads to unreliable predictions for the structures of larger clusters at this computational level.…”

Section: A Abn + -H 2 Omentioning

confidence: 94%

“…Previous low-level B3LYP/cc-pVDZ calculations for n ≤ 7 suggest the preference for the formation of a solvent network without proton transfer. 19 However, as will be shown below the small basis set and the lack of dispersion imply that these calculations do not properly reproduce the interactions in this cluster system and are thus not reliable. In addition, also the optical photodissociation spectra of ABN + -(H 2 O) n reported for n = 1-3 do not provide any decisive information about their structure.…”

Section: Introductionmentioning

confidence: 98%

“…In addition, also the optical photodissociation spectra of ABN + -(H 2 O) n reported for n = 1-3 do not provide any decisive information about their structure. 19 Second, we calculate in some detail the potential energy surface of the ABN + -H 2 O dimer (n = 1) to rationalize previous photoionization experiments of the neutral ABN-H 2 O dimer. 18,20,21 So far, three isomers of ABN-H 2 O in the neutral ground electronic state have been detected by resonance-enhanced multiphoton ionization (REMPI) and laser-induced fluorescence (LIF), 20,[22][23][24] and have been assigned by IR spectroscopy to the most stable NH-bound dimer and two less stable CN-bound isomers (linear and side).…”

Section: Introductionmentioning

confidence: 98%

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Microhydrated aromatic cluster cations: Binding motifs of 4-aminobenzonitrile-(H2O)n cluster cations with n ≤ 4

Schmies

Miyazaki

Fujii

et al. 2014

The Journal of Chemical Physics

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Infrared photodissociation (IRPD) spectra of mass-selected 4-aminobenzonitrile-(water)n cluster cations, ABN(+)-(H2O)n with n ≤ 4, recorded in the N-H and O-H stretch ranges are analyzed by quantum chemical calculations at the M06-2X/aug-cc-pVTZ level to determine the evolution of the initial microhydration process of this bifunctional aromatic cation in its ground electronic state. IRPD spectra of cold clusters tagged with Ar and N2 display higher resolution and allow for a clear-cut structural assignment. The clusters are generated in an electron impact source, which generates predominantly the most stable isomers. The IRPD spectra are assigned to single isomers for n = 1-3. The preferred cluster growth begins with sequential hydration of the two acidic NH protons of the amino group (n = 1-2), which is followed by attachment of secondary H2O ligands hydrogen-bonded to the first-shell ligands (n = 3-4). These symmetric and branched structures are more stable than those with a cyclic H-bonded solvent network. Moreover, in the size range n ≤ 4 the formation of a solvent network stabilized by strong cooperative effects is favored over interior ion hydration which is destabilized by noncooperative effects. The potential of the ABN(+)-H2O dimer is characterized in detail and supports the cluster growth derived from the IRPD spectra. Although the N-H bonds are destabilized by stepwise microhydration, which is accompanied by increasing charge transfer from ABN(+) to the solvent cluster, no proton transfer to the solvent is observed for n ≤ 4.

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Section: A Abn + -H 2 Omentioning

confidence: 94%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 98%

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Microhydrated aromatic cluster cations: Binding motifs of 4-aminobenzonitrile-(H2O)n cluster cations with n ≤ 4

Schmies

Miyazaki

Fujii

et al. 2014

The Journal of Chemical Physics

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Solvent Migration in Microhydrated Aromatic Aggregates: Ionization‐Induced Site Switching in the 4‐Aminobenzonitrile–Water Cluster

Nakamura

Schmies

Patzer

et al. 2014

Chemistry A European J

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The dependence of the preferred microhydration sites of 4-aminobenzonitrile (4ABN) on electronic excitation and ionization is determined through IR spectroscopy of its clusters with water (W) in a supersonic expansion and through quantum chemical calculations. IR spectra of neutral 4ABN and two isomers of its hydrogen-bonded (H-bonded) 4ABN-W complexes are obtained in the ground and first excited singlet states (S0, S1) through IR depletion spectroscopy associated with resonance-enhanced multiphoton ionization. Spectral analysis reveals that electronic excitation does not change the H-bonding motif of each isomer, that is, H2O binding either to the CN or the NH site of 4ABN, denoted as 4ABN-W(CN) and 4ABN-W(NH), respectively. The IR spectra of 4ABN(+)-W in the doublet cation ground electronic state (D0) are measured by generating them either in an electron ionization source (EI-IR) or through resonant multiphoton ionization (REMPI-IR). The EI-IR spectrum shows only transitions of the most stable isomer of the cation, which is assigned to 4ABN(+)-W(NH). The REMPI-IR spectrum obtained through isomer-selective resonant photoionization of 4ABN-W(NH) is essentially the same as the EI-IR spectrum. The REMPI-IR spectrum obtained by ionizing 4ABN-W(CN) is also similar to that of the 4ABN(+)-W(NH) isomer, but differs from that calculated for 4ABN(+)-W(CN), indicating that the H2O ligand migrates from the CN to the NH site upon ionization with a yield of 100%. The mechanism of this CN→NH site-switching reaction is discussed in the light of the calculated potential energy surface and the role of intracluster vibrational energy redistribution.

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Microsolvation of the 4‐Aminobenzonitrile Cation (ABN⁺) in a Nonpolar Solvent: IR Spectra of ABN⁺L_n (L=Ar and N₂, n≤4)

et al. 2012

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IR photodissociation (IRPD) spectra of mass-selected cluster ions of 4-aminobenzonitrile (ABN(+)) with up to four Ar and N2 ligands are recorded over the spectral range of the N-H stretching vibrations (ν(s/a)) of ABN(+) in its (2)B1 ground electronic state. ABN(+)-L(n) clusters are produced in an electron impact cluster ion source, which predominantly generates the most stable isomer of a given cluster ion. Vibrational frequency shifts of ν(s/a) provide information about the sequential microsolvation process of ABN(+) in a nonpolar solvent. In ABN(+)-(N2)n, the first two ligands fill a first subshell by forming hydrogen bonds to the acidic protons of the amino group, whereas further ligands bind more weakly to the aromatic ring (π bonds). Although the preferred cluster growth sequence in ABN(+)-Ar(n) is similar, several isomers are observed because the hydrogen bonds are only slightly stronger than the π bonds. Quantum chemical calculations at the M06-2X/aug-cc-pVTZ level confirm the cluster growth sequence derived from the IR spectra and provide further details of the intermolecular potential. The calculated binding energies of D0(H)=532 and 895 cm(-1) for hydrogen-bonded and D0(π)=512 and 530 cm(-1) for π-bonded Ar and N2 ligands are consistent with the observed photofragmentation branching ratios. Comparison between ABN(+)-L(n) and the corresponding clusters with the aniline cation demonstrates that the NH protons of the amino group become slightly more acidic upon H→CN substitution at the para position. Comparison between charged and neutral ABN((+))-L dimers indicates that ionization switches the preferred ion-ligand binding motif from π to hydrogen bonding.

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Photodissociation Dynamics of 4-Aminobenzonitrile⁺(Water)_nClusters

Cited by 7 publications

References 22 publications

Microhydrated aromatic cluster cations: Binding motifs of 4-aminobenzonitrile-(H2O)n cluster cations with n ≤ 4

Microhydrated aromatic cluster cations: Binding motifs of 4-aminobenzonitrile-(H2O)n cluster cations with n ≤ 4

Solvent Migration in Microhydrated Aromatic Aggregates: Ionization‐Induced Site Switching in the 4‐Aminobenzonitrile–Water Cluster

Microsolvation of the 4‐Aminobenzonitrile Cation (ABN⁺) in a Nonpolar Solvent: IR Spectra of ABN⁺L_n (L=Ar and N₂, n≤4)

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Photodissociation Dynamics of 4-Aminobenzonitrile+(Water)nClusters

Cited by 7 publications

References 22 publications

Microhydrated aromatic cluster cations: Binding motifs of 4-aminobenzonitrile-(H2O)n cluster cations with n ≤ 4

Microhydrated aromatic cluster cations: Binding motifs of 4-aminobenzonitrile-(H2O)n cluster cations with n ≤ 4

Solvent Migration in Microhydrated Aromatic Aggregates: Ionization‐Induced Site Switching in the 4‐Aminobenzonitrile–Water Cluster

Microsolvation of the 4‐Aminobenzonitrile Cation (ABN+) in a Nonpolar Solvent: IR Spectra of ABN+Ln (L=Ar and N2, n≤4)

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Photodissociation Dynamics of 4-Aminobenzonitrile⁺(Water)_nClusters

Microsolvation of the 4‐Aminobenzonitrile Cation (ABN⁺) in a Nonpolar Solvent: IR Spectra of ABN⁺L_n (L=Ar and N₂, n≤4)