Ab Initio Probing of the Ground State of Tetraradicals: Breakdown of Hund's Multiplicity Rule

The Journal of Physical Chemistry. a
Sudip Chattopadhyay

Abstract

The electronic structure of organic σ-type polyradical including 2,4,6-tridehydropyridine radical cation (246-TDHP) and three isomers of tetradehydrobenzene (TDHB) have been studied using a computationally robust and cost-effective second-order multireference perturbative model which provides a balanced treatment of nondynamic and dynamic contributions to the electron correlation problem in the ground or excited electronic states which are imperative for predicting structural properties (e.g., ground state multiplicity, energy gaps between high-spin and low-spin states, etc.) of polyradicals. Energy gaps are useful to capture insight into the degree of interaction between the radical sites. An important finding of this study is that the tetraradicals considered here possess singlet ground states, contrary to Hund's rule. Present findings are in close agreement with the available high-level ab initio estimates at attainable cost implying that a perturbative description of the systems is adequate. The impact of N+ on the nature of ground state for the 246-TDHP have also analyzed. The singlet-triplet energy gaps for 1245- and 1234-TDHB are smaller than for o-benzyne mainly due to the ring strain. 1235-TDHB is 14.42 and 11.05 kcal/...Continue Reading

References

Jun 21, 2003·The Journal of Organic Chemistry·Sundaram ArulmozhirajaAkira Yabe
Aug 31, 2004·The Journal of Chemical Physics·Celestino AngeliRenzo Cimiraglia
Mar 3, 2005·The Journal of Chemical Physics·Jamie M RintelmanMark S Gordon
Feb 14, 2006·The Journal of Chemical Physics·Celestino AngeliRenzo Cimiraglia
Apr 13, 2007·Journal of Chemical Information and Modeling·Karen L SchuchardtTheresa L Windus
Sep 25, 2007·Angewandte Chemie·Bartłomiej J JankiewiczHilkka I Kenttämaa
May 27, 2008·The Journal of Chemical Physics·Jon M MatxainLaura Gagliardi
Jul 16, 2008·The Journal of Chemical Physics·Uttam Sinha MahapatraRajat K Chaudhuri
Aug 15, 2008·Physical Chemistry Chemical Physics : PCCP·Cristopher CamachoHenryk A Witek
Nov 14, 2008·Angewandte Chemie·Bartłomiej J JankiewiczHilkka I Kenttämaa
Jan 7, 2009·The Journal of Chemical Physics·Sudip ChattopadhyayUttam Sinha Mahapatra
Jan 15, 2009·The Journal of Chemical Physics·Uttam Sinha MahapatraRajat K Chaudhuri
Jun 6, 2009·Physical Chemistry Chemical Physics : PCCP·Francesco A EvangelistaWesley D Allen
Oct 24, 2009·Physical Chemistry Chemical Physics : PCCP·David Casanova, Martin Head-Gordon
May 7, 2010·Physical Chemistry Chemical Physics : PCCP·Cristopher CamachoHenryk A Witek
Jan 12, 2011·Annual Review of Physical Chemistry·Garnet Kin-Lic Chan, Sandeep Sharma
Oct 18, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Sudip ChattopadhyayUttam Sinha Mahapatra
Jan 4, 2012·Journal of the American Chemical Society·Vanessa A GallardoHilkka I Kenttämaa
Jan 10, 2012·Chemical Reviews·Dmitry I LyakhRodney J Bartlett
Jan 21, 2012·The Journal of Chemical Physics·Shuneng MaoDebashis Mukherjee
Nov 22, 2012·Physical Chemistry Chemical Physics : PCCP·Franziska BellMartin Head-Gordon
Aug 31, 2013·Chemical Reviews·Peggy E WilliamsHilkka I Kenttämaa
Feb 18, 2015·Journal of Computational Chemistry·Avijit SenDebashis Mukherjee
Mar 6, 2015·Journal of Computational Chemistry·Sudip ChattopadhyayUttam Sinha Mahapatra
Sep 17, 2015·The Journal of Chemical Physics·Sandeep Sharma, Ali Alavi
Nov 18, 2015·Journal of Chemical Theory and Computation·Enhua XuShuhua Li
Feb 11, 2014·Journal of Chemical Theory and Computation·Nicholas J MayhallMartin Head-Gordon
Nov 13, 2012·Journal of Chemical Theory and Computation·Shu-Wei Chang, Henryk A Witek
Jul 14, 2016·Journal of Chemical Theory and Computation·Christopher J SteinMarkus Reiher
Oct 27, 2016·The Journal of Chemical Physics·Filipe MenezesHans-Joachim Werner
Dec 22, 2016·Accounts of Chemical Research·Laura GagliardiJunwei Lucas Bao

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