Probing different spin states in xylyl radicals and ions

Physical Chemistry Chemical Physics : PCCP
Mathias SteglichPatrick Hemberger

Abstract

Resonant one-color two-photon ionization spectroscopy and mass-selected threshold photoelectron spectroscopy were applied to study the electronic doublet states of the three xylyl (methyl-benzyl) radicals above 3.9 eV as well as the singlet and triplet states of the cations up to 10.5 eV. The experiments are complemented by quantum chemical calculations and Franck-Condon simulations to characterize the transitions and to identify the origin bands, allowing a precise determination of singlet-triplet splittings in the cations. Torsional motions of the methyl group notably affect the D0→ D3transition of m-xylyl. All other investigated transitions either lead to electronic states with very low rotational barriers or suffer from spectral broadening in excess of methyl torsional energy levels. The methyl internal rotational potential is faithfully reproduced with the most basic ab initio methods, yet hyperconjugation could not be identified as a significant force shaping them. Time-dependent density functional theory describes the excited electronic states better than wave function theory approaches, notably EOM-CCSD.

References

May 18, 1999·Journal of Molecular Spectroscopy·M H SuhT A Miller
Feb 16, 2007·The Journal of Physical Chemistry. a·N HansenT A Cool
Feb 19, 2008·Journal of the American Chemical Society·Patrik NeuhausWolfram Sander
May 5, 2009·The Journal of Physical Chemistry. a·Gabriel da SilvaJoseph W Bozzelli
Sep 18, 2009·The Journal of Physical Chemistry. a·Gabriel da SilvaJoseph W Bozzelli
Oct 3, 2009·The Journal of Physical Chemistry. a·Gabriel da Silva, Joseph W Bozzelli
Aug 24, 2010·The Journal of Chemical Physics·Markus MargrafIngo Fischer
Dec 7, 2010·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Michael SteinbauerAndras Bodi
Mar 26, 2011·Physical Chemistry Chemical Physics : PCCP·Yu SongJingsong Zhang
Jan 19, 2013·The Journal of Physical Chemistry. a·Shubin Liu
Apr 30, 2017·Physical Chemistry Chemical Physics : PCCP·A RöderR Mitrić
Aug 15, 2017·Physical Chemistry Chemical Physics : PCCP·Doory KimSeong Keun Kim
Sep 3, 2017·The Journal of Chemical Physics·Kai PachnerIngo Fischer
Oct 3, 2017·Journal of the American Chemical Society·Mathias SteglichPatrick Hemberger
Jan 16, 2018·The Journal of Physical Chemistry. a·Neil J ReillyTimothy W Schmidt

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Citations

Dec 13, 2018·Physical Chemistry Chemical Physics : PCCP·Mathias SteglichPatrick Hemberger
Oct 9, 2019·The Journal of Physical Chemistry. a·Florian HirschAnouk M Rijs
Dec 6, 2018·The Journal of Physical Chemistry. a·Andras Bodi, Patrick Hemberger

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Methods Mentioned

BETA
laser-induced fluorescence spectroscopy
electron exchange

Software Mentioned

EA
TDDFT
EOM
R2PI
PGOPHER
IP
SF
CCSD
Gaussian16
EE

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