This is a tale of a pair of a hydrogen bond donor and acceptor, namely the CH donor and sulphur acceptor, neither of which is a conventional hydrogen bond participant.

Polycyclic aromatic hydrocarbons (PAHs) play an important role in interstellar chemistry and are subject to high energy photons that can induce excitation, ionization, and fragmentation. Previous studies have demonstrated electronic relaxation of parent PAH monocations over 10–100 femtoseconds as a result of beyond-Born-Oppenheimer coupling between the electronic and nuclear dynamics. Here, we investigate three PAH molecules: fluorene, phenanthrene, and pyrene, using ultrafast XUV and IR laser pulses. Simultaneous measurements of the ion yields, ion momenta, and electron momenta as a function of laser pulse delay allow a detailed insight into the various molecular processes. We report relaxation times for the electronically excited PAH*, PAH+* and PAH2+* states, and show the time-dependent conversion between fragmentation pathways. Additionally, using recoil-frame covariance analysis between ion images, we demonstrate that the dissociation of the PAH2+ ions favors reaction pathways involving two-body breakup and/or loss of neutral fragments totaling an even number of carbon atoms.

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AbstractA general framework for the simulation of ultrafast pump-probe time resolved experiments based on Born-Oppenheimer molecular dynamics (BOMD) is presented. Interaction of the molecular species with a laser is treated by a simple maximum entropy distribution of the excited state occupancies. The latter decay of the electronic excitation into the vibrations is based on an on-the-fly estimation of the rate of the internal conversion, while the energy is distributed in a thermostat-like fashion. The approach was tested by reproducing the results of previous femtosecond studies on ethylene, naphthalene and new results for phenanthrene.

Non-covalent interactions are rapidly gaining interest as they are often crucial in determining the properties of materials, and key to supramolecular chemistry and to biochemistry. Non-covalent Polycyclic Aromatic Hydrocarbon (PAH) complexes are in particular relevant to astrochemistry and combustion chemistry where they are involved in the initial steps of condensation and soot formation, respectively. Here, we investigated non-covalent π-π stacking and CH-π interactions in naphthalene and acenaphthene clusters using high-resolution IR-UV spectroscopy in combination with quantum chemical calculations. We identified spectral shifts that occur upon complexation and thereby evaluated predicted potential energy surfaces. Although theory predicts a blueshift, a redshift is observed for the aliphatic CH-π interactions in the experimental spectrum of acenaphthene upon dimerization, indicating that CH-π interaction indeed affects the aliphatic bonds, while a blueshift is predicted, consequently theory deserves attention here. The results provide strong indications for a prevalent parallel naphthalene dimer, showing that π -π stacking interactions become significant for bicyclic and larger PAHs.

We investigated the dissociation of dications and trications of three polycyclic aromatic hydrocarbons (PAHs), fluorene, phenanthrene, and pyrene. PAHs are a family of molecules ubiquitous in space and involved in...

Benzene-(H2S) n (n = 1 and 2) clusters are the simplest prototype exemplifying the SH-π interaction. Electronic and infrared spectroscopies were applied to the benzene-(H2S) n clusters under the molecular beam condition. The S1–S0 electronic spectrum was observed by one-color resonant two-photon ionization combined with mass spectrometry. Ionization depletion infrared spectra were also observed in the CH and SH stretch regions. The isomer-selective infrared spectra demonstrated that at least two isomers of n = 1 coexist under the present beam condition, and both of them have the SH-π bound structures. One isomer showed a red-shift in the S1–S0 electronic transition relative to that of bare benzene, while the electronic transition of another isomer was slightly blue-shifted. For n = 2, we confirmed a structure, in which hydrogen-bonded H2S dimer is located on top of the aromatic ring.

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