The structure and binding energies of the van der Waals complexes of Ar and N2 with phenol and its cation, studied by high level <i>ab initio</i> and density functional theory calculations

Vincent, Mark A.; Hillier, Ian H.; Morgado, Claudio A.; Burton, Neil A.; Xiao, Shan

doi:10.1063/1.2828369

Cited by 23 publications

(17 citation statements)

References 32 publications

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“…In addition, high-level quantum chemical calculations of the potential energy surface in the S 0 state yield a -bonded global minimum, and it is unclear at present whether the H-bonded structure is a shallow local minimum or a transition state. [17][18][19][20] Comparison of rotational constants derived from a rotational band contour fit of the S 1 origin spectrum with ab initio rotational constants obtained at the MP2 / 6-31G͑d , p͒ level also support a -bonded ͑1 ͉ 0͒ geometry for n =1. 21 Meerts et al 6 presented the fully rotationally resolved electronic spectrum of the 7D-phenol-Ar 1 cluster, without a detailed structural analysis.…”

Section: Introductionmentioning

confidence: 67%

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: 67%

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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“…34,36 Other binding sites, such as H-bonding to the CH groups are less stable and thus not considered further. 34,35 Similar to the n = 1 complex, hole-burning spectroscopy reveals that the n = 2 REMPI spectrum in Fig. 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.…”

Section: Introductionmentioning

confidence: 91%

“…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%

“…Interestingly, the simulations reveal that at temperatures above melting and below boiling (evaporation) the less stable (20) isomer of benzene-Ar 2 is more abundant than the more stable (11) isomer due to entropy. 44 Spectroscopic 12,13,15 and theoretical studies 12,14,35,45 show that in the cationic D 0 state the H-bonded (H00) structure is the global minimum on the PhOH + -Ar potential and more stable than the p-bonded (10) local minimum. The dissociation energies of D 0 E 900 and 535 AE 3 cm À1 measured for (H00) 41,46 and (10) 47 are compatible with the interaction energies of 946 and 595 cm À1 obtained at the CCSD(T)/CBS level, respectively.…”

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confidence: 99%

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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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“…Comparison with related aromatic complexes, as well as computational studies reveal, however, that the p-binding site is by far the most stable non-hydrogen bonding site in this type of cluster. [8,65] Hence, we assign the experimental bands reported herein, which exhibit only minor complexation shifts at most, to isomers with newly added p-bound ligands.…”

mentioning

confidence: 89%

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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The structure and binding energies of the van der Waals complexes of Ar and N2 with phenol and its cation, studied by high level ab initio and density functional theory calculations

Cited by 23 publications

References 32 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

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

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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The structure and binding energies of the van der Waals complexes of Ar and N2 with phenol and its cation, studied by high level ab initio and density functional theory calculations

Cited by 23 publications

References 32 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

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

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