Bonding in Singlet and Triplet Butalene:: Insights from Spin-Coupled Theory

David L. Cooper; Peter B. Karadakov; Brian J. Duke

doi:10.1021/acs.jpca.5b00522

Bonding in Singlet and Triplet Butalene: Insights from Spin-Coupled Theory

David L. Cooper^*, Peter B. Karadakov, Brian J. Duke

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Spin-coupled (SC, equivalent to full generalized valence bond) calculations for the 1Ag ground state of butalene at its optimal D2h planar geometry show that cross-ring Dewar-like modes of spin coupling are of comparable importance to the more usually considered Kekulé-like modes. There are marked similarities to the SC description of one of the isomers of benzo[1,2:4,5]dicyclobutadiene. A complication for both of these systems is the existence of SC solutions in which some of the orbitals resemble in- and out-of-phase combinations of semilocalized atom-centered orbitals. The lowest triplet state, for which a nonplanar C2v geometry is preferred, is somewhat more straightforward to analyze: the SC description of the 3B2 state is dominated by a very simple pattern of two π bonds and two well-localized triplet-coupled orbitals.

Original language	English
Pages (from-to)	2169-2175
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	119
Issue number	10
DOIs	https://doi.org/10.1021/acs.jpca.5b00522
Publication status	Published - 12 Mar 2015

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title = "Bonding in Singlet and Triplet Butalene:: Insights from Spin-Coupled Theory",

abstract = "Spin-coupled (SC, equivalent to full generalized valence bond) calculations for the 1Ag ground state of butalene at its optimal D2h planar geometry show that cross-ring Dewar-like modes of spin coupling are of comparable importance to the more usually considered Kekul{\'e}-like modes. There are marked similarities to the SC description of one of the isomers of benzo[1,2:4,5]dicyclobutadiene. A complication for both of these systems is the existence of SC solutions in which some of the orbitals resemble in- and out-of-phase combinations of semilocalized atom-centered orbitals. The lowest triplet state, for which a nonplanar C2v geometry is preferred, is somewhat more straightforward to analyze: the SC description of the 3B2 state is dominated by a very simple pattern of two π bonds and two well-localized triplet-coupled orbitals.",

author = "Cooper, {David L.} and Karadakov, {Peter B.} and Duke, {Brian J.}",

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language = "English",

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TY - JOUR

T1 - Bonding in Singlet and Triplet Butalene:

T2 - Insights from Spin-Coupled Theory

AU - Cooper, David L.

AU - Karadakov, Peter B.

AU - Duke, Brian J.

PY - 2015/3/12

Y1 - 2015/3/12

N2 - Spin-coupled (SC, equivalent to full generalized valence bond) calculations for the 1Ag ground state of butalene at its optimal D2h planar geometry show that cross-ring Dewar-like modes of spin coupling are of comparable importance to the more usually considered Kekulé-like modes. There are marked similarities to the SC description of one of the isomers of benzo[1,2:4,5]dicyclobutadiene. A complication for both of these systems is the existence of SC solutions in which some of the orbitals resemble in- and out-of-phase combinations of semilocalized atom-centered orbitals. The lowest triplet state, for which a nonplanar C2v geometry is preferred, is somewhat more straightforward to analyze: the SC description of the 3B2 state is dominated by a very simple pattern of two π bonds and two well-localized triplet-coupled orbitals.

AB - Spin-coupled (SC, equivalent to full generalized valence bond) calculations for the 1Ag ground state of butalene at its optimal D2h planar geometry show that cross-ring Dewar-like modes of spin coupling are of comparable importance to the more usually considered Kekulé-like modes. There are marked similarities to the SC description of one of the isomers of benzo[1,2:4,5]dicyclobutadiene. A complication for both of these systems is the existence of SC solutions in which some of the orbitals resemble in- and out-of-phase combinations of semilocalized atom-centered orbitals. The lowest triplet state, for which a nonplanar C2v geometry is preferred, is somewhat more straightforward to analyze: the SC description of the 3B2 state is dominated by a very simple pattern of two π bonds and two well-localized triplet-coupled orbitals.

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U2 - 10.1021/acs.jpca.5b00522

DO - 10.1021/acs.jpca.5b00522

M3 - Article

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SN - 1089-5639

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EP - 2175

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 10

ER -

Bonding in Singlet and Triplet Butalene: Insights from Spin-Coupled Theory

Abstract

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