Two-dimensional laser induced fluorescence spectroscopy of van der Waals complexes: fluorobenzene-Arn (n=1,2)

The technique of two-dimensional laser induced fluorescence (2D-LIF) spectroscopy has been used to observe the van der Waals complexes fluorobenzene-Ar and fluorobenzene-Ar2 in the region of their S1-S0 electronic origins. The 2D-LIF spectral images reveal a number of features assigned to the van der Waals vibrations in S0 and S1. An advantage of 2D-LIF spectroscopy is that the LIF spectrum associated with a particular species may be extracted from an image. This is illustrated for fluorobenzene-Ar. The S1 van der Waals modes observed in this spectrum are consistent with previous observations using mass resolved resonance enhanced multiphoton ionisation techniques. For S0, the two bending modes previously observed using a Raman technique were observed along with three new levels. These agree exceptionally well with ab initio calculations. The Fermi resonance between the stretch and bend overtone has been analysed in both the S0 and S1 states, revealing that the coupling is stronger in S0 than in S1. For fluorobenzene-Ar2 the 2D-LIF spectral image reveals the S0 symmetric stretch van der Waals vibration to be 35.0 cm−1, closely matching the value predicted based on the fluorobenzene-Ar van der Waals stretch frequency. Rotational band contour analysis has been performed on the fluorobenzene-Ar math transition to yield a set of S1 rotational constants A′ = 0.05871 ± 0.00014 cm−1, B′ = 0.03803 ± 0.00010 cm−1, and C′ = 0.03103 ± 0.00003 cm−1. The rotational constants imply that in the S1 00 level the Ar is on average 3.488 Å from the fluorobenzene centre of mass and displaced from it towards the centre of the ring at an angle of ∼6° to the normal. The rotational contour for fluorobenzene-Ar2 was predicted using rotational constants calculated on the basis of the fluorobenzene-Ar geometry and compared with the experimental contour. The comparison is poor which, while due in part to expected saturation effects, suggests the presence of another band lying beneath the contour

Two dimensional laser induced fluorescence spectroscopy: a powerful technique for elucidating rovibronic structure in electronic transitions of polyatomic molecules

We demonstrate the power of high resolution, two dimensional laser induced fluorescence (2D-LIF) spectroscopy for observing rovibronic transitions of polyatomic molecules. The technique involves scanning a tunable laser over absorption features in the electronic spectrum while monitoring a segment, in our case 100 cm−1 wide, of the dispersed fluorescence spectrum. 2D-LIF images separate features that overlap in the usual laser induced fluorescence spectrum. The technique is illustrated by application to the S1–S0 transition in fluorobenzene. Images of room temperature samples show that overlap of rotational contours by sequence band structure is minimized with 2D-LIF allowing a much larger range of rotational transitions to be observed and high precision rotational constants to be extracted. A significant advantage of 2D-LIF imaging is that the rotational contours separate into their constituent branches and these can be targeted to determine the three rotational constants individually. The rotational constants determined are an order of magnitude more precise than those extracted from the analysis of the rotational contour and we find the previously determined values to be in error by as much as 5%. Comparison with earlier ab initio calculations of the S0 and S1 geometries reveals that the CCSD/6–311G** and RI-CC2/def2-TZVPP levels of theory predict the rotational constants, and hence geometries, with comparable accuracy. Two ground state Fermi resonances were identified by the distinctive patterns that such resonances produce in the images. 2D-LIF imaging is demonstrated to be a sensitive method capable of detecting weak spectral features, particularly those that are otherwise hidden beneath stronger bands. The sensitivity is demonstrated by observation of the three isotopomers of fluorobenzene-d1 in natural abundance in an image taken for a supersonically cooled sample. The ability to separate some of the 13C isotopomers in natural abundance is also demonstrated. The equipment required to perform 2D-LIF imaging with sufficient resolution to resolve the rotational features of large polyatomics is available from commercial suppliers

Intermolecular vibrations of fluorobenzene-Ar up to 130 cm-1 in the ground electronic state

Sixteen intermolecular vibrational levels of the S0 state of the fluorobenzene-Ar van der Waals complex have been observed using dispersed fluorescence. The levels range up to -130 cm−1 in vibrational energy. The vibrational energies have been modelled using a complete set of harmonic and quartic anharmonic constants and a cubic anharmonic coupling between the stretch and long axis bend overtone that becomes near ubiquitous at higher energies. The constants predict the observed band positions with a root mean square deviation of 0.04 cm−1. The set of vibrational levels predicted by the constants, which includes unobserved bands, has been compared with the predictions of ab initio calculations, which include all vibrational levels up to 70–75 cm−1. There are small differences in energy, particularly above 60 cm−1, however, the main differences are in the assignments and are largely due to the limitations of assigning the ab initio wave-functions to a simple stretch, bend, or combination when the states are mixed by the cubic anharmonic coupling. The availability of these experimental data presents an opportunity to extend ab initio calculations to higher vibrational energies to provide an assessment of the accuracy of the calculated potential surface away from the minimum. The intermolecular modes of the fluorobenzene-Ar2 trimer complex have also been investigated by dispersed fluorescence. The dominant structure is a pair of bands with a -35 cm−1 displacement from the origin band. Based on the set of vibrational modes calculated from the fluorobenzene-Ar frequencies, they are assigned to a Fermi resonance between the symmetric stretch and symmetric short axis bend overtone. The analysis of this resonance provides a measurement of the coupling strength between the stretch and short axis bend overtone in the dimer, an interaction that is not directly observed. The coupling matrix elements determined for the fluorobenzene-Ar stretch-long axis bend overtone and stretch-short axis bend overtone couplings are remarkably similar (3.8 cm−1 cf. 3.2 cm−1). Several weak features seen in the fluorobenzene-Ar2 spectrum have also been assigned