Characterizing centrosymmetric two-ring PAHs using jet-cooled high resolution mid-infrared laser spectroscopy and anharmonic quantum chemical calculations.

Abstract

The presence of Polycyclic Aromatic Hydrocarbon (PAH) molecules in the interstellar medium, recently confirmed by the detection of cyano-naphthalenes, has renewed the interest of extensive spectroscopic and physical-chemistry studies on such large species. The present study reports the jet-cooled rovibrational infrared study of three centrosymmetric two-ring PAH molecules, viz., naphthalene (C10H8), [1,5] naphthyridine (C8H6N2), and biphenyl (C12H10), in the in-plane ring C-H bending (975-1035cm-1) and C-C ring stretching (1580-1620cm-1) regions. For the two most rigid PAHs, the accuracy of spectroscopic parameters derived in ground and several excited states (six for naphthalene and six for [1,5] naphthyridine) has significantly improved the literature values. In addition, comparison between experiments and quantum chemical calculations confirms the predictive power of the corrected calculated rotational parameters. The more flexible structure of biphenyl makes the analysis of high resolution jet-cooled spectra of ν19 and ν23 modes recorded at about 1601 and 1013cm-1, respectively, particularly challenging. The presence of three torsional vibrations below 120cm-1 together with small values of the rotational constants prevented us from determining the ground and v19 = 1 excited rotational constants independently. In the ν23 band region, the presence of two bands rotationally resolved and separated by only 0.8cm-1 raises the question of possible splittings due to a large amplitude motion, most probably the torsion of the aliphatic bond between the two phenyl rings.