Spectroscopy on triphenylamine and its van der Waals complexes
نویسندگان
چکیده
Both vibrationally and rotationally resolved spectra of the S, + So transition in jet-cooled triphenylamine (TPA) around 340320 nm are reported. Medium resolutton spectra (0.5-l .O cm-’ resolution) are recorded using ( 1 + 1 )-resonance enhanced multi photon iomzation (REMPI) with mass selective time-of-flight (TOF) detection in a pulsed molecular beam apparatus. The origin ofthe S,+ So transition is at 29520.7 cm-‘, higher than halfway to the iomzation potential (IP) found at 6.89 eV. A vibrational progression m the symmetric torsion mode ( 1 14 cm-‘) as well as in the symmetric C-N stretching mode (280 cm-‘) is observed m the electronic spectra. The spectrum of the most abundant isomer of the TPA-Ar (TPA-Kr ) complexes is blue-shifted by 2 11 cmI ( 2 16 cm-’ ) with respect to the spectrum of the free TPA molecule High-resolution (the resolution mamly being determined by the natural linewidth of the transition, i.e. 36 MHz) spectra are recorded using laser Induced fluorescence (LIF) in a cw molecular beam apparatus. Individual rotational transitions are resolved and the spectrum shows unambiguously that TPA is a symmetric top molecule. The rotational constant B” m the So state of TPA is equal to B”=403.7 f0.5 MHz. Upon S,+So excitation both B and C mcrease with 7.4 2 0.1 MHz and 2.8 k 0.1 MHz, respectively. The spectrum of the blue-shifted TPA-Ar isomer is the spectrum of a symmetric top molecule as well, and therefore the Ar atom has to be located on the C3 symmetry axis, either on top of or underneath the umbrella formed by the phenyl rmgs. It appears that when Ar or Kr forms a complex with TPA, the first Ar, Kr. atom goes preferentially in a position on the C, symmetry axis of TPA, a position which causes an abnormal blueshift of the spectrum. With the first rare-gas atom located m this special position, the second rare-gas atom is forced into a “normal” position, i.e. above one of the phenyl rings, causing a normal red-shift with respect to the TPA-Ar complex.
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