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Magnetic coupling in bis-nitronylnitroxide radicals: The role of aromatic bridges
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10.1063/1.3077029
/content/aip/journal/jcp/130/9/10.1063/1.3077029
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/9/10.1063/1.3077029

Figures

Image of FIG. 1.
FIG. 1.

The two fragmentation schemes of the bis-nitronyl nitroxide molecules. Different combinations of the numbered fragments of (a) and (b) gives the cases of Table II.

Image of FIG. 2.
FIG. 2.

1,4-bis-nitronylnitroxide benzene (para) (a) and 1,3-bis-nitronylnitroxide benzene (meta) (b).

Image of FIG. 3.
FIG. 3.

energy splitting vs the number of MOs considered in the CI (the number of doubly occupied MOs is 52), for the para and meta phenyl bridged bis nitronyl nitroxide diradicals (Fig. 1) from CI calculations using the SCF, CASSCF, canonical, and localized MOs in the two-fragment (2F) scheme (upper) and localized CASSCF MOs in the n-fragment schemes of Table II (lower). Experimental data from Refs. 43 and 44.

Image of FIG. 4.
FIG. 4.

1,4-bisnitronyl benzene (N-para) (a) and 1,3-bisnitronyl benzene (N-meta) (b).

Image of FIG. 5.
FIG. 5.

energy splitting vs the number of MOs considered in the CI (the number of doubly occupied MOs is 25), for the N-PARA and N-META species (Fig. 4) from CI calculations using the SCF, CASSCF, canonical and localized MOs in the two-fragment (2F) and three-fragment schemes of Table II.

Image of FIG. 6.
FIG. 6.

Excess spin Mulliken population analysis for the N-meta and N-para systems in the triplet state with . First row: UHF calculation, second row (bold): CI calculation.

Image of FIG. 7.
FIG. 7.

MO diagram for the para biradical. Left: antisymmetric manifold. Right: symmetric manifold.

Image of FIG. 8.
FIG. 8.

MO diagram for the meta biradical. Left: antisymmetric manifold. Right: symmetric manifold.

Image of FIG. 9.
FIG. 9.

Examples of the three kinds of E configurations. From left to right: neutral spin polarization, neutral without spin polarization, CT. The labels j, x, a, and b refer to core, empty, and magnetic MOs, respectively.

Tables

Generic image for table
Table I.

Composition of the CI space in terms of the number of core, magnetic, and empty MOs (Ref. 27).

Generic image for table
Table II.

Fragmentation cases based on the scheme of Fig. 1 (see text). The MOs localized on the fragments not listed in the last column (neglected MO) are included in the one-electron space of the CI calculations.

Generic image for table
Table III.

Absolute and relative energies (Hartree) of the triplet state for several types of calculations for the N-para and N-meta species of Fig. 4.

Generic image for table
Table IV.

The overlap between the magnetic MOs as resulting from ROHF of the triplet state and the benzene MOs.

Generic image for table
Table V.

CI results for several choices of configurations from those reported in Table I. SD is Slater determinant.

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/content/aip/journal/jcp/130/9/10.1063/1.3077029
2009-03-06
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Magnetic coupling in bis-nitronylnitroxide radicals: The role of aromatic bridges
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/9/10.1063/1.3077029
10.1063/1.3077029
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