Measuring Intermolecular Binding Energies by Laser Spectroscopy

Richard, K and Maity, Surajit and Geraldine, F and Samuel, L (2017) Measuring Intermolecular Binding Energies by Laser Spectroscopy. CHIMIA International Journal for Chemistry, 71 (1). pp. 7-12. ISSN 0009-4293

Full text not available from this repository. (Request a copy)


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.

[error in script]
IITH Creators:
IITH CreatorsORCiD
Item Type: Article
Uncontrolled Keywords: Dispersive Interactions; Hydrogen Bonding; Intermolecular Interactions; Stimulated Emission Pumping
Subjects: Chemistry
Divisions: Department of Chemistry
Depositing User: Team Library
Date Deposited: 09 Mar 2017 06:44
Last Modified: 26 Aug 2017 04:09
Publisher URL:
OA policy:
Related URLs:

Actions (login required)

View Item View Item
Statistics for RAIITH ePrint 3082 Statistics for this ePrint Item