σ-Aromaticity in H3+ and Li3+: Insights from ring-current maps

R.W.A. Havenith; F. de Proft; P.W. Fowler; P. Geerlings

σ-Aromaticity in H3+ and Li3+: Insights from ring-current maps

R.W.A. Havenith, F. de Proft, P.W. Fowler, P. Geerlings

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Abstract

Putative s-aromaticity of the clusters H3+ and Li3+ is investigated by computation of ring-current maps in the ab initio ipsocentric approach. Although H3+ shows a marked diatropic ring-current and can be considered s aromatic on the magnetic criterion, Li3+ shows no global current and is non-aromatic on this criterion, in spite of its electron count and negative NICS value. The difference in magnetic response is interpreted in terms of orbital energies using the ipsocentric model: in Li3+ the diatropic HOMO-LUMO excitation is opposed by paratropic excitations to higher unoccupied orbitals; in H3+ this cancellation does not occur.

Original language	Undefined/Unknown
Pages (from-to)	391-396
Number of pages	6
Journal	Chemical Physics Letters
Volume	407
Publication status	Published - 2005

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title = "σ-Aromaticity in H3+ and Li3+: Insights from ring-current maps",

abstract = "Putative s-aromaticity of the clusters H3+ and Li3+ is investigated by computation of ring-current maps in the ab initio ipsocentric approach. Although H3+ shows a marked diatropic ring-current and can be considered s aromatic on the magnetic criterion, Li3+ shows no global current and is non-aromatic on this criterion, in spite of its electron count and negative NICS value. The difference in magnetic response is interpreted in terms of orbital energies using the ipsocentric model: in Li3+ the diatropic HOMO-LUMO excitation is opposed by paratropic excitations to higher unoccupied orbitals; in H3+ this cancellation does not occur.",

author = "R.W.A. Havenith and {de Proft}, F. and P.W. Fowler and P. Geerlings",

year = "2005",

language = "Undefined/Unknown",

volume = "407",

pages = "391--396",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - σ-Aromaticity in H3+ and Li3+: Insights from ring-current maps

AU - Havenith, R.W.A.

AU - de Proft, F.

AU - Fowler, P.W.

AU - Geerlings, P.

PY - 2005

Y1 - 2005

N2 - Putative s-aromaticity of the clusters H3+ and Li3+ is investigated by computation of ring-current maps in the ab initio ipsocentric approach. Although H3+ shows a marked diatropic ring-current and can be considered s aromatic on the magnetic criterion, Li3+ shows no global current and is non-aromatic on this criterion, in spite of its electron count and negative NICS value. The difference in magnetic response is interpreted in terms of orbital energies using the ipsocentric model: in Li3+ the diatropic HOMO-LUMO excitation is opposed by paratropic excitations to higher unoccupied orbitals; in H3+ this cancellation does not occur.

AB - Putative s-aromaticity of the clusters H3+ and Li3+ is investigated by computation of ring-current maps in the ab initio ipsocentric approach. Although H3+ shows a marked diatropic ring-current and can be considered s aromatic on the magnetic criterion, Li3+ shows no global current and is non-aromatic on this criterion, in spite of its electron count and negative NICS value. The difference in magnetic response is interpreted in terms of orbital energies using the ipsocentric model: in Li3+ the diatropic HOMO-LUMO excitation is opposed by paratropic excitations to higher unoccupied orbitals; in H3+ this cancellation does not occur.

M3 - Article

SN - 0009-2614

VL - 407

SP - 391

EP - 396

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -