2004
DOI: 10.1021/jp049462f
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Electronic Structures and Spectroscopic Properties of 6π-Electron Ring Molecules and Ions E2N2 and E42+ (E = S, Se, Te)

Abstract: The electronic structures and molecular properties of square-planar 6-electron ring molecules and ions E2N2 and E4 2+ (E = S, Se, Te) were studied using various ab initio methods and density functionals. All species were found to contain singlet diradical character in their electronic structures. Detailed analysis of the CAS wave function of S2N2 in terms of different valence bond structures gives largest weight for a Lewis-type singlet diradical VB structure in which the two unpaired electrons reside on nitr… Show more

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Cited by 58 publications
(94 citation statements)
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“…We have recently shown that even at the equilibrium geometry, the RHF wave function of S2N2 displays a singlet instability. 16 Because a symmetry-broken UHF solution can be found, it is perfectly valid to state that the strong electron correlations described by Jung et al 25 Before turning attention to the molecular properties of S2N2 and the related heavier chalcogen containing species SeSN2 and Se2N2, we seek to answer another open question, whether the diradical character in S2N2 should be attributed to nitrogen or to sulfur atoms. Previous VB calculations have come to two different conclusions, [20][21][22][23][24] whereas our recent MO-theory based wave function analyses indicated that the diradical character of S2N2 in its equilibrium geometry can be unquestionably addressed to the nitrogen atoms.…”
Section: Resultsmentioning
confidence: 97%
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“…We have recently shown that even at the equilibrium geometry, the RHF wave function of S2N2 displays a singlet instability. 16 Because a symmetry-broken UHF solution can be found, it is perfectly valid to state that the strong electron correlations described by Jung et al 25 Before turning attention to the molecular properties of S2N2 and the related heavier chalcogen containing species SeSN2 and Se2N2, we seek to answer another open question, whether the diradical character in S2N2 should be attributed to nitrogen or to sulfur atoms. Previous VB calculations have come to two different conclusions, [20][21][22][23][24] whereas our recent MO-theory based wave function analyses indicated that the diradical character of S2N2 in its equilibrium geometry can be unquestionably addressed to the nitrogen atoms.…”
Section: Resultsmentioning
confidence: 97%
“…However, this lack of symmetry-broken spin-unrestricted DFT solution cannot be held as a definite proof of a non-existent diradical character because DFT solutions are found to be stable even for some of the obvious diradicals such as ozone whose diradical character has been found to be 26% by ab initio methods. 16 In ab initio theory, the instability of the spinrestricted SCF solution is a direct indication of the quality of the wave function, whereas within the DFT framework of electronic structure theory it mirrors the capability of the exchange-correlation functional to describe the electron density with a single Slater determinant comprised of Kohn-Sham (KS) orbitals. If the exact exchange-correlation functional were available, a single Slater determinant of KS orbitals would be adequate to describe even pure diradical systems and, hence, no lower-energy spin-unrestricted solutions would therefore be found.…”
Section: Resultsmentioning
confidence: 99%
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