Modern valence-bond-like representations of selected D-6h "aromatic" rings

J. Grant Hill; David L. Cooper; Peter B. Karadakov

doi:10.1021/jp057458d

Modern valence-bond-like representations of selected D-6h "aromatic" rings

J. Grant Hill, David L. Cooper, Peter B. Karadakov

Chemistry

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

Abstract

Starting from CASSCF( 6,6)/6-31G(d,p) wave functions, we consider different valence-bond (VB)-like interpretations of the d electron systems for various ( constrained) "benzene-like" D-6h rings, exploiting the invariance of the total wave function to arbitrary nonsingular transformations of the active orbitals. Quantities obtained rather directly from the various calculations provide a fairly consistent ordering of the degree of aromaticity: C6H6 similar to B-6 > N-6 > Al-6 similar to Si6H6 > P-6. Representations based on mutually orthogonal orbitals are found to be somewhat less satisfactory than those that have no such constraints on the overlaps between the active orbitals.

Original language	English
Pages (from-to)	7913-7917
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	110
Issue number	25
DOIs	https://doi.org/10.1021/jp057458d
Publication status	Published - 29 Jun 2006

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10.1021/jp057458d

http://dx.doi.org/10.1021/jp057458d

Cite this

@article{cbe0325aefb54b5eaf87747bb096f283,

title = "Modern valence-bond-like representations of selected D-6h {"}aromatic{"} rings",

abstract = "Starting from CASSCF( 6,6)/6-31G(d,p) wave functions, we consider different valence-bond (VB)-like interpretations of the d electron systems for various ( constrained) {"}benzene-like{"} D-6h rings, exploiting the invariance of the total wave function to arbitrary nonsingular transformations of the active orbitals. Quantities obtained rather directly from the various calculations provide a fairly consistent ordering of the degree of aromaticity: C6H6 similar to B-6 > N-6 > Al-6 similar to Si6H6 > P-6. Representations based on mutually orthogonal orbitals are found to be somewhat less satisfactory than those that have no such constraints on the overlaps between the active orbitals.",

author = "Hill, {J. Grant} and Cooper, {David L.} and Karadakov, {Peter B.}",

year = "2006",

month = jun,

day = "29",

doi = "10.1021/jp057458d",

language = "English",

volume = "110",

pages = "7913--7917",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "25",

}

TY - JOUR

T1 - Modern valence-bond-like representations of selected D-6h "aromatic" rings

AU - Hill, J. Grant

AU - Cooper, David L.

AU - Karadakov, Peter B.

PY - 2006/6/29

Y1 - 2006/6/29

N2 - Starting from CASSCF( 6,6)/6-31G(d,p) wave functions, we consider different valence-bond (VB)-like interpretations of the d electron systems for various ( constrained) "benzene-like" D-6h rings, exploiting the invariance of the total wave function to arbitrary nonsingular transformations of the active orbitals. Quantities obtained rather directly from the various calculations provide a fairly consistent ordering of the degree of aromaticity: C6H6 similar to B-6 > N-6 > Al-6 similar to Si6H6 > P-6. Representations based on mutually orthogonal orbitals are found to be somewhat less satisfactory than those that have no such constraints on the overlaps between the active orbitals.

AB - Starting from CASSCF( 6,6)/6-31G(d,p) wave functions, we consider different valence-bond (VB)-like interpretations of the d electron systems for various ( constrained) "benzene-like" D-6h rings, exploiting the invariance of the total wave function to arbitrary nonsingular transformations of the active orbitals. Quantities obtained rather directly from the various calculations provide a fairly consistent ordering of the degree of aromaticity: C6H6 similar to B-6 > N-6 > Al-6 similar to Si6H6 > P-6. Representations based on mutually orthogonal orbitals are found to be somewhat less satisfactory than those that have no such constraints on the overlaps between the active orbitals.

U2 - 10.1021/jp057458d

DO - 10.1021/jp057458d

M3 - Article

SN - 1089-5639

VL - 110

SP - 7913

EP - 7917

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 25

ER -