Calculated and Experimental Structures of the p-Difluorobenzene-(H2O)n=1-3 Clusters in Their Different Electronic States and Inference for Ionic Nucleophilic Substitution

Brenner, V.; Martrenchard‐Barra, S.; Millié, P.; Dedonder‐Lardeux, C.; Jouvet, Christophe; Solgadi, D.

doi:10.1021/j100016a019

Cited by 32 publications

(30 citation statements)

References 5 publications

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“…8,14 An upper limit of 818 cm excitation. The energy of two photons at this wavelength is well above the pDFB-H 2 O ionization potential so that fragmentation could occur from both excited and ionic states; however, a two-color 1 + 1Ј REMPI experiment established that the dissociation observed in the one-color experiment occurs from 5 1 in S 1 .…”

Section: A Dfb-water Binding Energiesmentioning

confidence: 99%

“…10 The S 1 ← S 0 transition of the pDFB-H 2 O complex has been studied using both one and two-color 1 + 1 REMPI. 8,14 The pDFB-H 2 O origin transition is 169 cm −1 higher in energy than the pDFB monomer origin: The complex is more weakly bound in the excited electronic state. Similar blueshifts were reported for the other vibronic bands: 6 0 1 ͑+169 cm −1 ͒, 8 0 2 ͑+176 cm −1 ͒, and 5 0 1 ͑+158 cm −1 ͒.…”

Section: Introductionmentioning

confidence: 97%

“…7 This is consistent with earlier calculations. 8,9 The remaining H atom appears to lie out of the plane. This change in the nature of the aromatic-water interaction has led us to explore the complexes of water with the series of difluorobenzenes ͑DFBs͒, viz.…”

Section: Introductionmentioning

confidence: 99%

“…A number of studies of the pDFB-H 2 O complex have been reported, [7][8][9]14,15 however, studies of the ortho and meta isomers appear restricted to a Ph.D thesis. 10 The S 1 ← S 0 transition of the pDFB-H 2 O complex has been studied using both one and two-color 1 + 1 REMPI.…”

Section: Introductionmentioning

confidence: 99%

“…15 The ionization potential of pDFB-H 2 O was determined using two color 1+1Ј REMPI to be 72 450Ϯ 50 cm −1 , 14 although Brenner et al note that as their calculations suggest a significant difference in geometry between the neutral and ionic states, the measured ionization threshold may be higher than the adiabatic ionization potential. 8 The S 1 ← S 0 transitions of the mDFB-H 2 O and oDFB-H 2 O complex have been studied using mass resolved REMPI. 10 The mDFB-H 2 O origin transition is 92 cm −1 blueshifted from the mDFB monomer, while the oDFB-H 2 O origin transition is 105 cm −1 blueshifted from the oDFB monomer.…”

Section: Introductionmentioning

confidence: 99%

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A velocity map ion imaging study of difluorobenzene-water complexes: Binding energies and recoil distributions

Bellm

Leeuwen

Lawrance

2008

The Journal of Chemical Physics

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The binding energies of the p-, m-, and o-difluorobenzene-H2O complexes have been measured by velocity map ion imaging to be 922±10, 945±10, and 891±4cm−1, respectively. The lack of variation provides circumstantial evidence for water binding to the three isomers via the same interaction, viz. an in-plane O–H⋯F hydrogen bond to one of the fluorine atoms on the ring, with a second, weaker interaction of the water O atom with an ortho hydrogen, as determined previously for the p-difluorobenzene-H2O complex [Kang et al., J. Phys. Chem. A 109, 767 (2005)]. The ground state binding energies for the difluorobenzene-H2O complexes are ∼5%–11% larger than that for benzene-H2O, where binding occurs to the π electrons out-of-plane. However, in the S1 state the binding energies of the o- and p-difluorobenzene-H2O complexes are smaller than the benzene-H2O value, raising an interesting question about whether the geometry at the global energy minimum remains in-plane in the excited electronic states of these two complexes. Recoil energy distributions for dissociation of p-difluorobenzene-H2O have been measured from the 31¯, 52¯, and 3151¯ levels of the excited electronic state. These levels are 490, 880, and 1304cm−1, respectively, above the dissociation threshold. Within the experimental uncertainty, the recoil energy distributions are the same for dissociation from these three states, with average recoil energies of ∼100cm−1. These recoil energies are 60% larger than was observed for the dissociation of p-difluorobenzene-Ar, which is a substantially smaller increase than the 400% seen in a comparable study of dissociation within the triplet state for pyrazine-Ar, -H2O complexes. The majority of the available energy is partitioned into vibration and rotation of the fragments.

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Section: A Dfb-water Binding Energiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A velocity map ion imaging study of difluorobenzene-water complexes: Binding energies and recoil distributions

Bellm

Leeuwen

Lawrance

2008

The Journal of Chemical Physics

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Binding Energies of the π‐Stacked Anisole Dimer: New Molecular Beam—Laser Spectroscopy Experiments and CCSD(T) Calculations

Řezáč

Nachtigallová

Mazzoni

et al. 2015

Chemistry A European J

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Among noncovalent interactions, π-π stacking is a very important binding motif governed mainly by London dispersion. Despite its importance, for instance, for the structure of bio-macromolecules, the direct experimental measurement of binding energies in π-π stacked complexes has been elusive for a long time. Only recently, an experimental value for the binding energy of the anisole dimer was presented, determined by velocity mapping ion imaging in a two-photon resonant ionisation molecular beam experiment. However, in that paper, a discrepancy was already noted between the obtained experimental value and a theoretical estimate. Here, we present an accurate recalculation of the binding energy based on the combination of the CCSD(T)/CBS interaction energy and a DFT-D3 vibrational analysis. This proves unambiguously that the previously reported experimental value is too high and a new series of measurements with a different, more sensitive apparatus was performed. The new experimental value of 1800±100 cm(-1) (5.15±0.29 kcal mol(-1)) is close to the present theoretical prediction of 5.04±0.40 kcal mol(-1). Additional calculations of the properties of the cationic and excited states involved in the photodissociation of the dimer were used to identify and rationalise the difficulties encountered in the experimental work.

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Monte Carlo growth method: application to molecular clusters

Bertolus¹,

Brenner²,

Millié³

et al. 1997

Z Phys D - Atoms, Molecules and Clusters

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Calculated and Experimental Structures of the p-Difluorobenzene-(H2O)n=1-3 Clusters in Their Different Electronic States and Inference for Ionic Nucleophilic Substitution

Cited by 32 publications

References 5 publications

A velocity map ion imaging study of difluorobenzene-water complexes: Binding energies and recoil distributions

A velocity map ion imaging study of difluorobenzene-water complexes: Binding energies and recoil distributions

Binding Energies of the π‐Stacked Anisole Dimer: New Molecular Beam—Laser Spectroscopy Experiments and CCSD(T) Calculations

Monte Carlo growth method: application to molecular clusters

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