Conformational explosion: Understanding the complexity of short chain para-dialkylbenzene potential energy surfaces

The Journal of Chemical Physics
Piyush MishraTimothy S Zwier

Abstract

The single-conformation ultraviolet and infrared spectroscopy of three short-chain para-dialkylbenzenes (para-diethylbenzene, para-dipropylbenzene, and para-dibutylbenzene) is reported for the jet-cooled, isolated molecules. The present study builds off previous work on single-chain n-alkylbenzenes, where an anharmonic local mode Hamiltonian method was developed to account for stretch-bend Fermi resonance in the alkyl CH stretch region [D. P. Tabor et al., J. Chem. Phys. 144, 224310 (2016)]. The jet-cooled molecules are interrogated using laser-induced fluorescence (LIF) excitation, fluorescence dip infrared spectroscopy, and dispersed fluorescence. The LIF spectra in the S1 ← S0 origin region show a dramatic increase in the number of resolved transitions with increasing length of the alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an "egg carton" shaped potential energy surface. A combination of electronic frequency shift and alkyl CH stretch infrared spectra is used to generate a consistent set of conformational assignments. Using these experim...Continue Reading

References

Jul 26, 2006·The Journal of Physical Chemistry. B·Jeffery B KlaudaRichard W Pastor
Dec 3, 2008·The Journal of Chemical Physics·Nathan R PillsburyTimothy S Zwier
Aug 22, 2012·Angewandte Chemie·Nils O B LüttschwagerMartin A Suhm
Jun 17, 2016·The Journal of Chemical Physics·Daniel P TaborEdwin L Sibert

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Citations

Oct 19, 2019·Physical Chemistry Chemical Physics : PCCP·Piyush MishraTimothy S Zwier
Mar 18, 2021·Physical Chemistry Chemical Physics : PCCP·Piyush MishraTimothy S Zwier

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