Singlet-triplet energy splitting and excited states of phenylnitrene

The Journal of Physical Chemistry. a
Michael Winkler

Abstract

The vertical and adiabatic singlet-triplet energy splittings (Delta E ST) of phenylnitrene were computed by a variety of multireference configuration interaction and perturbation theory methods employing basis sets of up to quadruple-xi quality and extrapolation to the complete basis set limit. The vertical and adiabatic energy gaps are 18.9 and 15.9 kcal mol (-1), respectively, the latter in reasonable agreement with the revised experimental value of 15.1 +/- 0.2 kcal mol (-1). The energy difference between both states at the geometry of the a (1)A 2 singlet state was also considered and amounts to 13.8 kcal mol (-1). In obtaining accurate state energy splittings, basis set completeness turns out to be a more important issue than the level of dynamical electron correlation treatment. Density functional theory that is frequently employed to investigate phenylnitrenes and their rearrangements yields varying results and, depending on the functional, gives adiabatic energy differences between 9 and 16 kcal mol (-1). The b (1)A 1 state has a similar geometry as the ground state of 1 and is 31 kcal mol (-1) higher in energy. According to best estimates, the next higher singlet states, c (1)A 1 and d (1)B 1, are 57 and 72 kcal mol (-...Continue Reading

References

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Citations

Jul 5, 2013·Accounts of Chemical Research·Michael Winkler, Wolfram Sander
Jan 2, 2013·Journal of the American Chemical Society·Nathan J RauPaul G Wenthold
Oct 18, 2014·Journal of the American Chemical Society·David KvaskoffCurt Wentrup
Apr 2, 2011·The Journal of Organic Chemistry·Weston Thatcher Borden
Sep 30, 2015·Journal of Computational Chemistry·Klara EdelHolger F Bettinger
Oct 12, 2010·Organic & Biomolecular Chemistry·Holger F Bettinger, Matthias Filthaus
Aug 7, 2009·The Journal of Physical Chemistry. a·Neloni R WijeratnePaul G Wenthold
Jul 25, 2017·Journal of the American Chemical Society·Ekram HossainPaul G Wenthold
Nov 16, 2018·Journal of the American Chemical Society·Joel Mieres-PerezWolfram Sander
Oct 10, 2018·The Journal of Physical Chemistry. a·Didier BéguéCurt Wentrup
Feb 25, 2017·Chemical Reviews·Curt Wentrup
Nov 30, 2021·Mass Spectrometry Reviews·Cory J ConderPaul G Wenthold

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