Protobranching as repulsion-induced attraction: a prototype for geminal stabilization

Physical Chemistry Chemical Physics : PCCP
Justin P JoyceAnthony K Rappè

Abstract

Noncovalent interactions are traditionally defined within the context of their attractive components, such as electrostatics and dispersion. Sources of molecular strain are derived through the destabilization of Coulombic and exchange repulsion. Due to this binary designation, the underlying origin of geminal stability with respect to alkanes (referred to as protobranching) has been an active subject for debate between these competing perspectives. We recast this stabilization as a complementary (Gestalt) interaction between dispersion and exchange repulsion, each impacting the other. We use triplet hydrogen and argon dimer as foundational van der Waals adducts to develop a procedure for the visualization and quantification of both exchange repulsion, ΔρSCF, and medium-range correlation, ΔΔρ, as perturbations in electron density. We use the framework of the DFT-D3 correction to reproduce the shape of the dispersion potential at medium range and successfully model the trend in stability for the eighteen isomers of octane with a diverse series of functionals: BLYP, B3LYP, BP86, PBE, and PBE0. Collectively, our findings show that protobranching is a manifestation of steric repulsion-reduction in vibrational enthalpy and medium-ran...Continue Reading

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Jul 18, 2001·Journal of the American Chemical Society·J Ma, S Inagaki
Sep 5, 2002·Journal of the American Chemical Society·Mutasem Omar SinnokrotC David Sherrill
Oct 29, 2005·The Journal of Chemical Physics·Axel D Becke, Erin R Johnson
Jan 28, 2006·The Journal of Organic Chemistry·Scott Gronert
Mar 11, 2006·Chemistry : a European Journal·Richard F W Bader
May 13, 2006·The Journal of Chemical Physics·Erin R Johnson, Axel D Becke
Aug 4, 2006·The Journal of Physical Chemistry. a·Elena JakubikovaElliot R Bernstein
Aug 11, 2006·Organic Letters·Matthew D WodrichPaul von Ragué Schleyer
Jul 4, 2007·Chemistry : a European Journal·Matthew D WodrichPaul von Ragué Schleyer
Oct 24, 2007·The Journal of Chemical Physics·Axel D Becke, Erin R Johnson
Jun 7, 2008·Physical Chemistry Chemical Physics : PCCP·Stefan GrimmeJens Antony
Oct 18, 2008·The Journal of Physical Chemistry. a·Matthew D WodrichClémence Corminboeuf
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Jeng-Da Chai, Martin Head-Gordon
Apr 7, 2010·Physical Review Letters·Katarzyna PernalKrzysztof Szalewicz
May 1, 2010·Chemistry : a European Journal·Carl R KemnitzAdam F Nielsen
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Apr 26, 2011·Journal of Chemical Theory and Computation·Julia Contreras-GarcíaWeitao Yang
Sep 28, 2012·The Journal of Physical Chemistry. a·Lawrence S Bartell
Jan 25, 2013·The Journal of Chemical Physics·Christoph Riplinger, Frank Neese
Mar 5, 2013·The Journal of Physical Chemistry. a·Jan M L Martin
Apr 16, 2013·Journal of the American Chemical Society·Anthony J Stone
Jul 23, 2013·Chemistry : a European Journal·Carl R Kemnitz
Aug 6, 2013·Journal of the American Chemical Society·William C McKee, Paul von Ragué Schleyer
Dec 17, 2014·The Journal of Chemical Physics·M J Gillan
Aug 10, 2015·The Journal of Chemical Physics·Robert M ParrishC David Sherrill
Dec 11, 2012·Journal of Chemical Theory and Computation·Amy AustinKyle Throssell
Feb 19, 2016·Journal of Chemical Theory and Computation·Dimitrios G LiakosFrank Neese
Apr 15, 2016·Chemical Reviews·Stefan GrimmeChristoph Bannwarth
Apr 26, 2016·Accounts of Chemical Research·Steven E WheelerAnalise C Doney
May 21, 2016·The Journal of Physical Chemistry Letters·Daniel G A SmithC David Sherrill

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