Benchmark experimental gas-phase intermolecular dissociation energies by the SEP-R2PI method

Richard Knochenmuss, Rajeev K. Sinha, Samuel Leutwyler

Research output: Contribution to journalReview articlepeer-review

5 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)189-211
Number of pages23
JournalAnnual Review of Physical Chemistry
Publication statusPublished - 20-04-2020

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry


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