Measuring Intermolecular Binding Energies by Laser Spectroscopy
The ground-state dissociation energy, D0(S0), of isolated intermolecular complexes in the gas phase is a fundamental measure of the interaction strength between the molecules. We have developed a three-laser, triply resonant pump-dump-probe technique to measure dissociation energies of jet...
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Swiss Chemical Society
2017-02-01
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| Series: | CHIMIA |
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| Online Access: | https://www.chimia.ch/chimia/article/view/1553 |
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| author | Richard Knochenmuss Surajit Maity Géraldine Féraud Samuel Leutwyler |
| author_facet | Richard Knochenmuss Surajit Maity Géraldine Féraud Samuel Leutwyler |
| author_sort | Richard Knochenmuss |
| collection | DOAJ |
| description |
The ground-state dissociation energy, D0(S0), of isolated intermolecular complexes in the gas phase is a fundamental measure of the interaction strength between the molecules. We have developed a three-laser, triply resonant pump-dump-probe technique to measure
dissociation energies of jet-cooled M•S complexes, where M is an aromatic chromophore and S is a closed-shell 'solvent' molecule. Stimulated emission pumping (SEP) via the S0?S1 electronic transition is used to precisely 'warm' the complex by populating high
vibrational levels v" of the S0 state. If the deposited energy E(v") is less than D0(S0), the complex remains intact, and is then mass- and isomer-selectively detected by resonant two-photon ionization (R2PI) with a third (probe) laser. If
the pumped level is above D0(S0), the hot complex dissociates and the probe signal disappears. Combining the fluorescence or SEP spectrum of the cold complex with the SEP breakoff of the hot complex brackets D0(S0). The UV chromophores 1-naphthol
and carbazole were employed; these bind either dispersively via the aromatic rings, or form a hydrogen bond via the -OH or -NH group. Dissociation energies have been measured for dispersively bound complexes with noble gases (Ne, Kr, Ar, Xe), diatomics (N2, CO), alkanes (methane
to n-butane), cycloalkanes (cyclopropane to cycloheptane), and unsaturated compounds (ethene, benzene). Hydrogen-bond dissociation energies have been measured for H2O, D2O, methanol, ethanol, ethers (oxirane, oxetane), NH3 and ND3.
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| first_indexed | 2024-12-24T00:18:18Z |
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| language | deu |
| last_indexed | 2024-12-24T00:18:18Z |
| publishDate | 2017-02-01 |
| publisher | Swiss Chemical Society |
| record_format | Article |
| series | CHIMIA |
| spelling | doaj.art-91eb53dd59384f099356d99dd518fb092022-12-21T17:24:40ZdeuSwiss Chemical SocietyCHIMIA0009-42932673-24242017-02-01711-210.2533/chimia.2017.7Measuring Intermolecular Binding Energies by Laser SpectroscopyRichard Knochenmuss0Surajit Maity1Géraldine Féraud2Samuel Leutwyler3Universität Bern, Departement für Chemie und Biochemie, Freiestrasse 3 CH-3012 BernDept. of Chemistry, IIT Hyderabad Kandi, Sangareddy-502285, Telangana, IndiaLERMA, Sorbonne Universités UPMC University Paris 06, Observatorie de Paris PSL Research University, CNRS, F-75252 ParisUniversität Bern, Departement für Chemie und Biochemie, Freiestrasse 3 CH-3012 Bern;, Email: leutwyler@iac.unibe.ch The ground-state dissociation energy, D0(S0), of isolated intermolecular complexes in the gas phase is a fundamental measure of the interaction strength between the molecules. We have developed a three-laser, triply resonant pump-dump-probe technique to measure dissociation energies of jet-cooled M•S complexes, where M is an aromatic chromophore and S is a closed-shell 'solvent' molecule. Stimulated emission pumping (SEP) via the S0?S1 electronic transition is used to precisely 'warm' the complex by populating high vibrational levels v" of the S0 state. If the deposited energy E(v") is less than D0(S0), the complex remains intact, and is then mass- and isomer-selectively detected by resonant two-photon ionization (R2PI) with a third (probe) laser. If the pumped level is above D0(S0), the hot complex dissociates and the probe signal disappears. Combining the fluorescence or SEP spectrum of the cold complex with the SEP breakoff of the hot complex brackets D0(S0). The UV chromophores 1-naphthol and carbazole were employed; these bind either dispersively via the aromatic rings, or form a hydrogen bond via the -OH or -NH group. Dissociation energies have been measured for dispersively bound complexes with noble gases (Ne, Kr, Ar, Xe), diatomics (N2, CO), alkanes (methane to n-butane), cycloalkanes (cyclopropane to cycloheptane), and unsaturated compounds (ethene, benzene). Hydrogen-bond dissociation energies have been measured for H2O, D2O, methanol, ethanol, ethers (oxirane, oxetane), NH3 and ND3. https://www.chimia.ch/chimia/article/view/1553Dispersive interactionsHydrogen bondingIntermolecular interactionsStimulated emission pumping |
| spellingShingle | Richard Knochenmuss Surajit Maity Géraldine Féraud Samuel Leutwyler Measuring Intermolecular Binding Energies by Laser Spectroscopy CHIMIA Dispersive interactions Hydrogen bonding Intermolecular interactions Stimulated emission pumping |
| title | Measuring Intermolecular Binding Energies by Laser Spectroscopy |
| title_full | Measuring Intermolecular Binding Energies by Laser Spectroscopy |
| title_fullStr | Measuring Intermolecular Binding Energies by Laser Spectroscopy |
| title_full_unstemmed | Measuring Intermolecular Binding Energies by Laser Spectroscopy |
| title_short | Measuring Intermolecular Binding Energies by Laser Spectroscopy |
| title_sort | measuring intermolecular binding energies by laser spectroscopy |
| topic | Dispersive interactions Hydrogen bonding Intermolecular interactions Stimulated emission pumping |
| url | https://www.chimia.ch/chimia/article/view/1553 |
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