Noncovalent interactions: a challenge for experiment and theory

Molecular Clusters of π-Systems: Theoretical Studies of Structures, Spectra, and Origin of Interaction Energies

London dispersion, which constitutes the attractive part of the famous van der Waals potential, has long been underappreciated in molecular chemistry as an important element of structural stability, and thus affects chemical reactivity and catalysis. This negligence is due to the common notion that dispersion is weak, which is only true for one pair of interacting atoms. For increasingly larger structures, the overall dispersion contribution grows rapidly and can amount to tens of kcal mol(-1) . This Review collects and emphasizes the importance of inter- and intramolecular dispersion for molecules consisting mostly of first row atoms. The synergy of experiment and theory has now reached a stage where dispersion effects can be examined in fine detail. This forces us to reconsider our perception of steric hindrance and stereoelectronic effects. The quantitation of dispersion energy donors will improve our ability to design sophisticated molecular structures and much better catalysts.

London Dispersion in Molecular Chemistry—Reconsidering Steric Effects

▪ Abstract Various aspects of molecular solvation are reviewed from the perspective provided by gas-phase aromatic solute-(solvent)n clusters. Particular emphasis is placed on hydrogen-bonded clusters, varying from 1:1 aromatic-H2O complexes up to clusters containing several water or methanol molecules. Recent advances in experimental methods for obtaining accurate structures, binding energies, and intermolecular and intramolecular vibrational spectra are highlighted. Many of these methods provide size and conformation selectivity and can be readily extended to both ground and electronically excited neutral states. The π hydrogen bond, hydrogen bonding to aromatic alcohols, water complexation to indole and its derivatives, and the hydrogen-bonded networks of benzene-(H2O)n and benzene-(CH3OH)n clusters are reviewed in special detail.

The spectroscopy of solvation in hydrogen-bonded aromatic clusters

The Spectroscopy of Solvation in Hydrogen-Bonded Aromatic Clusters

ZEKE Spectroscopy of Complexes and Clusters

The two-colour, two-photon (1 + 1′) resonance-enhanced multiphoton ionisation (REMPI) spectrum of the S1 state of the hydrogen-bonded phenol–methanol complex has been recorded. The region around the S1 origin is in good agreement with previously reported spectra. In this work, further discussion of this region is presented and all the observed spectral features are attributed to intermolecular vibrations (and combinations) of a single conformal isomer. Additionally, further bands have been observed in the higher energy region and are assigned to intramolecular (phenol-localised) modes in combination with intermolecular vibrations.Zero-kinetic-energy (ZEKE) photoelectron spectra have been recorded using different intermediate vibrational levels in the S1 state. The spectrum recorded via the vibrationless level of the S1 state shows beautiful structure and indicates a substantial change in complex geometry on ionisation. The observed structure is dominated by progressions of a low-frequency intermolecular bending vibration (34 cm–1) in combination with other intermolecular vibrations. In particular, the intermolecular stretch (278 cm–1) demonstrates a progression, each component of which is in combination with progressions of the low-frequency bending mode. Excitation via other intermediate, intermolecular vibronic states also gives rise to structured spectra and these lead to the assignment of the six intermolecular vibrational frequencies of the phenol–methanol cation. In contrast, excitation via the intramolecular phenol ν6a level gives rise to a featureless spectrum. It is proposed that the latter observation is due to rapid intramolecular vibrational relaxation (IVR) in the S1 state. The energy of the lowest band observed in the ZEKE spectra exciting via the S1 vibrationless level, the intermolecular stretch and also two other intermolecular vibrations, in all cases allowed a (field-corrected) adiabatic ionisation energy of 63 207 ± 4 cm–1(7.8367 ± 0.0005 eV) to be derived.

Zero-kinetic-energy (ZEKE) photoelectron spectroscopy of the hydrogen-bonded phenol–methanol complex

The hydrogen-bonded phenol-ethanol complex has been studied using both two-color resonant-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) photoelectron spectroscopy. The REMPI spectrum shows vibrational structure which can be assigned to low-frequency intermolecular modes on the S 1 origin and in combination with intramolecular (phenol-localized) vibrations of the S 1 electronic state: a reinterpretation of the low-energy region of the REMPI spectrum gives the frequency of the intermolecular stretch in the S 1 state as 162 cm -1

Vibrational spectroscopy of the phenol-ethanol cation

Chapter 9. Recent applications and developments in ZEKE spectroscopy

Vibrational spectroscopy of the microsolvated phenol cation : phenol-dimethyl ether

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