The Dissociation Energy of the Benzene - Argon van der Waals Complex Determined by Velocity Map Imaging

Sampson, Rebecca K; Lawrance, Warren D.

doi:10.1071/ch03050

Cited by 33 publications

(37 citation statements)

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“…9. Among these are van der Waals complexes M·S of aromatic chromophores M such as benzene, 10 paradifluorobenzene, 11,12 phenol, 13 anisole, 14 indole, 15 dibenzop-dioxin, 16 and carbazole [17][18][19] with noble gases (S = Ne, Ar, Kr, Xe), or small closed-shell molecules (S = N 2 , CO, CH 4 ). 19 In these cases, linear correlation of D 0 (S 0 ) with the polarizability of the S atom or molecule was observed, as expected from London dispersion theory.…”

Section: Introductionmentioning

confidence: 99%

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Maity

Knochenmuss

Holzer

et al. 2016

The Journal of Chemical Physics

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Articles you may be interested inInfluences of the propyl group on the van der Waals structures of 4-propylaniline complexes with one and two argon atoms studied by electronic and cationic spectroscopy J. Chem. Phys. 143, 034308 (2015); 10.1063/1.4927004The weak hydrogen bond in the fluorobenzene-ammonia van der Waals complex: Insights into the effects of electron withdrawing substituents on π versus in-plane bonding J. Chem. Phys. 126, 154319 (2007) The 1-naphthol·cyclopropane intermolecular complex is formed in a supersonic jet and investigated by resonant two-photon ionization (R2PI) spectroscopy, UV holeburning, and stimulated emission pumping (SEP)-R2PI spectroscopy. Two very different structure types are inferred from the vibronic spectra and calculations. In the "edge" isomer, the OH group of 1-naphthol is directed towards a C-C bond of cyclopropane, the two ring planes are perpendicular. In the "face" isomer, the cyclopropane is adsorbed on one of the π-aromatic faces of the 1-naphthol moiety, the ring planes are nearly parallel. Accurate ground-state intermolecular dissociation energies D 0 were measured with the SEP-R2PI technique. The D 0 (S 0 ) of the edge isomer is bracketed as 15.35 ± 0.03 kJ/mol, while that of the face isomer is 16.96 ± 0.12 kJ/mol. The corresponding excited-state dissociation energies D 0 (S 1 ) were evaluated using the respective electronic spectral shifts. Despite the D 0 (S 0 ) difference of 1.6 kJ/mol, both isomers are observed in the jet in similar concentrations, so they must be separated by substantial potential energy barriers. Intermolecular binding energies, D e , and dissociation energies, D 0 , calculated with correlated wave function methods and two dispersion-corrected density-functional methods are evaluated in the context of these results. The density functional calculations suggest that the face isomer is bound solely by dispersion interactions. Binding of the edge isomer is also dominated by dispersion, which makes up two thirds of the total binding energy. Published by AIP Publishing. [http://dx

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Section: Introductionmentioning

confidence: 99%

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Maity

Knochenmuss

Holzer

et al. 2016

The Journal of Chemical Physics

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“…More recently, Lawrance and co-workers 34 have provided a more accurate D 0 = 3.77 ± 0.08 kJ/mol using velocity map imaging (VMI). While the lower limit of the PFI-MATI measurement agrees with the VMI value, the breakdown measurement 32 yields a much smaller dissociation energy (cf.…”

Section: Benzene·argonmentioning

confidence: 99%

“…Since 2000, the groups of Lawrance 16,17,34,35 Figure 8. In Figure 8( [38][39][40][41] Similar to the ionization-based appearance potential, ion breakdown, MATI and VMI methods described in Sections 3.2 -3.4, the method is based on the detection of the M + ·S ion and is mass-(and isotope-) specific.…”

Section: Velocity Map Imaging (Vmi)mentioning

confidence: 99%

Experimental and Theoretical Determination of Dissociation Energies of Dispersion-Dominated Aromatic Molecular Complexes

et al. 2016

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The dissociation energy (D 0 ) of an isolated and cold molecular complex in the gas-phase is a fundamental measure of the strength of the intermolecular interactions between its constituent moieties. Accurate D 0 values are important for the understanding of intermolecular bonding, for benchmarking high-level theoretical calculations and for the parametrization of force-field models used in fields ranging from crystallography to biochemistry. We re- 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59

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“…The initial energy is well defined ͑522 cm −1 ͒, 16 the final vibrational energy is known ͑0 cm −1 ͒, and the dissociation energy is also known ͑335 cm −1 ͒. 23 The energy available for rotation and translation of the products is thus 187 cm −1 . If the translational energy distribution is known, then the rotational energy distribution is readily calculated by conservation of energy.…”

Section: A Velocity Map Imagingmentioning

confidence: 99%

“…[19][20][21][22] The binding energy of the complex has recently been measured to be 314± 7 cm −1 in S 0 , i.e., 335± 7 cm −1 in S 1 . 23 Dispersed fluorescence from 6 1 , which at 522 cm −1 lies above the dissociation threshold, was reported by Stephenson and Rice to show bands only due to 6 1 . 16 However, we have recently examined dispersed fluorescence from 6 1 at improved resolution and identified emission of the benzene product in the 0 0 state.…”

Section: Introductionmentioning

confidence: 99%

Rotational distributions following van der Waals molecule dissociation: Comparison between experiment and theory for benzene–Ar

Sampson

Bellm

McCaffery

et al. 2005

The Journal of Chemical Physics

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On the authors' and employers' webpages: There are no format restrictions; files prepared and/or formatted by AIP or its vendors (e.g., the PDF, PostScript, or HTML article files published in the online journals and proceedings) may be used for this purpose. If a fee is charged for any use, AIP permission must be obtained. An appropriate copyright notice must be included along with the full citation for the published paper and a Web link to AIP's official online version of the abstract. The translational energy release distribution for dissociation of benzene-Ar has been measured and, in combination with the 6 1 0 rotational contour of the benzene product observed in emission, used to determine the rotational J,K distribution of 0 0 benzene products formed during dissociation from 6 1 . Significant angular momentum is transferred to benzene on dissociation. The 0 0 rotational distribution peaks at J = 31 and is skewed to low K : J average = 27, ͉K͉ average = 10.3. The average angle between the total angular momentum vector and the unique rotational axis is determined to be 68°. This indicates that benzene is formed tumbling about in-plane axes rather than in a frisbeelike motion, consistent with Ar "pushing off" benzene from an off-center position above or below the plane. The J distribution is very well reproduced by angular momentum model calculations based on an equivalent rotor approach ͓A. J. McCaffery, M. A. Osborne, R. J. Marsh, W. D. Lawrance, and E. R. Waclawik, J. Chem. Phys. 121, 1694 ͑2004͔͒, indicating that angular momentum constraints control the partitioning of energy between translation and rotation. Calculations for p-difluorobenzene-Ar suggest that the equivalent rotor model can provide a reasonable prediction of both J and K distributions in prolate ͑or near prolate͒ tops when dissociation leads to excitation about the unique, in-plane axis. Calculations for s-tetrazine-Ar require a small maximum impact parameter to reproduce the comparatively low J values seen for the s-tetrazine product. The three sets of calculations show that the maximum impact parameter is not necessarily equal to the bond length of the equivalent rotor and must be treated as a variable parameter. The success of the equivalent rotor calculations argues that angular momentum constraints control the partitioning between rotation and translation of the products.

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The Dissociation Energy of the Benzene - Argon van der Waals Complex Determined by Velocity Map Imaging

Cited by 33 publications

References 0 publications

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Experimental and Theoretical Determination of Dissociation Energies of Dispersion-Dominated Aromatic Molecular Complexes

Rotational distributions following van der Waals molecule dissociation: Comparison between experiment and theory for benzene–Ar

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