Single vibronic level emission spectroscopy of the low-lying electronic states of NiI

Ayles, Victoria L.; Muzangwa, Lloyd; Reid, Scott A.

doi:10.1016/j.cplett.2010.08.016

Cited by 6 publications

(1 citation statement)

References 28 publications

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“…84 A 1% mixture of the chlorobenzene precursor in He, generated by passing the high purity gas over a sample of chlorobenzene held in a temperature controlled bath, at a total pressure of typically ∼1-2 bar was expanded from the 1.0 mm diameter nozzle of the pulsed valve, and passed through a 1.0 mm diameter skimmer into the differentially pumped flight tube of a 1-m linear TOFMS, described in some detail in our previous work. [85][86][87] The flight tube was evacuated by a 250 L/s turbomolecular pump, with a gate valve used to isolate the detector, which was kept under vacuum at all times. The main chamber was evacuated with a water-baffled diffusion pump (Varian VHS-4).…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

On π-stacking, C-H/π, and halogen bonding interactions in halobenzene clusters: Resonant two-photon ionization studies of chlorobenzene

Muzangwa

Nyambo

Uhler

et al. 2012

The Journal of Chemical Physics

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Noncovalent interactions such as hydrogen bonding, π-π stacking, CH/π interactions, and halogen bonding play crucial roles in a broad spectrum of chemical and biochemical processes, and can exist in cooperation or competition. Here we report studies of the homoclusters of chlorobenzene, a prototypical system where π-π stacking, CH/π interactions, and halogen bonding interactions may all be present. The electronic spectra of chlorobenzene monomer and clusters (Clbz)(n) with n = 1-4 were obtained using resonant 2-photon ionization in the origin region of the S(0)-S(1) (ππ*) state of the monomer. The cluster spectra show in all cases a broad spectrum whose center is redshifted from the monomer absorption. Electronic structure calculations aid in showing that the spectral broadening arises in large part from inhomogeneous sources, including the presence of multiple isomers and Franck-Condon (FC) activity associated with geometrical changes induced by electronic excitation. Calculations at the M06-2x/aug-cc-pVDZ level find in total five minimum energy structures for the dimer, four π-stacked structures, and one T-shaped, and six representative minimum energy structures were found for the trimer. The calculated time-dependent density functional theory spectra using range-separated and meta-GGA hybrid functionals show that these isomers absorb over a range that is roughly consistent with the breadth of the experimental spectra, and the calculated absorptions are redshifted with respect to the monomer transition, in agreement with experiment. Due to the significant geometry change in the electronic transition, where for the dimer a transition from a parallel displaced to sandwich structure occurs with a reduced separation of the two monomers, significant FC activity is predicted in low frequency intermolecular modes.

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