Benchmark Experimental Gas-Phase Intermolecular Dissociation Energies by the SEP-R2PI Method

Sinha, Rajeev K (2020) Benchmark Experimental Gas-Phase Intermolecular Dissociation Energies by the SEP-R2PI Method. Annual Review of Physical Chemistry, 71. pp. 189-211. ISSN 0066-426X

[img] PDF
8730DisplayPdf.pdf - Published Version
Restricted to Registered users only

Download (1MB) | Request a copy

Abstract

The gas-phase ground-state dissociation energy D0(S0) of an isolated and cold bimolecular complex is a fundamental measure of the intermolecular interaction strength between its constituents. Accurate D0 values are important for the understanding of intermolecular bonding, for benchmarking high-level theoretical calculations, and for the parameterization of dispersion-corrected density functionals or force-field models that are used in fields ranging from crystallography to biochemistry. We review experimental measurements of the gas-phase D0(S0) and D0(S1) values of 55 different M·S complexes, where M is a (hetero)aromatic molecule and S is a closed-shell solvent atom or molecule. The experiments employ the triply resonant SEP-R2PI laser method, which involves M-centered (S0 → S1)electronic excitation, followed by S1 → S0 stimulated emission spanning a range of S0 state vibrational levels. At sufficiently high vibrational energy,vibrational predissociation of the M·S complex occurs. A total of 49 dissociation energies were bracketed to within ≤1.0 kJ/mol, providing a large experimental database of accurate noncovalent interactions

Item Type: Article
Uncontrolled Keywords: Intermolecular binding energy; Intermolecular dissociation energy; Noncovalent interactions; London dispersion; Hydrogen bond
Subjects: Departments at MU > Atomic Molecular Physics
Depositing User: KMC Library
Date Deposited: 06 Jul 2020 06:18
Last Modified: 06 Jul 2020 06:18
URI: http://eprints.manipal.edu/id/eprint/155428

Actions (login required)

View Item View Item