TY - JOUR

T1 - Magnetism and structure of graphene nanodots with interiors modified by boron, nitrogen, and charge

AU - Philpott, Michael R.

AU - Kawazoe, Yoshiyuki

PY - 2012/8/7

Y1 - 2012/8/7

N2 - The properties (geometry, spin, and charge distribution) of a series of flat hexagonal zigzag edged graphene nanodots (GNDs), with interiors modified by centrally located substituent atoms boron and nitrogen and by positive and negative charge, have been calculated using ab initio density functional theory. The doped series X-GND has the stoichiometry C6m 2-1XH 6m, zigzag size index m 2, 4, 6, 8, 10 and substituent X B or N. The undoped parents C6m 2H 6m with m 8 have spin paired ground states and the parent m 10 has a spin polarized singlet ground state with edges that alternate α- and β-spin. The spin on the substituent atom decreases to zero with size index m and magnetization builds on the edges of all the X-GND. This demonstrates translocation of substituent spin and a proximity or directional effect for small m as the edges show different degrees of magnetization. For the largest X-GND (m 10) the magnetization on edges resembles the calculated triplet S 1(a) configuration of the parent (four edge spins up and two down) and has a higher apparent symmetry than the C 2v point group of X-GND. For charged (m 10) GNDs the edge magnetization has strength comparable to the parent on two parallel edges and weak on the other four in a perimeter pattern that resembles the triplet S 1(b) configuration of the undoped parent and not the ground configuration of the isoelectronic X-GND molecule. Many of the results can be interpreted by simple Kekule valence bond structures for an unpaired spin on a network where the substituent site group symmetry is not compatible with the perimeter. A deeper understanding is provided by the properties of the Kohn-Sham orbitals. The calculations of the X-doped GNDs reveal limitations in the use of the hex-radical hypothesis of the parent ground state to systems where foreign atoms lower symmetry and perturb the π- and σ-bond manifolds.

AB - The properties (geometry, spin, and charge distribution) of a series of flat hexagonal zigzag edged graphene nanodots (GNDs), with interiors modified by centrally located substituent atoms boron and nitrogen and by positive and negative charge, have been calculated using ab initio density functional theory. The doped series X-GND has the stoichiometry C6m 2-1XH 6m, zigzag size index m 2, 4, 6, 8, 10 and substituent X B or N. The undoped parents C6m 2H 6m with m 8 have spin paired ground states and the parent m 10 has a spin polarized singlet ground state with edges that alternate α- and β-spin. The spin on the substituent atom decreases to zero with size index m and magnetization builds on the edges of all the X-GND. This demonstrates translocation of substituent spin and a proximity or directional effect for small m as the edges show different degrees of magnetization. For the largest X-GND (m 10) the magnetization on edges resembles the calculated triplet S 1(a) configuration of the parent (four edge spins up and two down) and has a higher apparent symmetry than the C 2v point group of X-GND. For charged (m 10) GNDs the edge magnetization has strength comparable to the parent on two parallel edges and weak on the other four in a perimeter pattern that resembles the triplet S 1(b) configuration of the undoped parent and not the ground configuration of the isoelectronic X-GND molecule. Many of the results can be interpreted by simple Kekule valence bond structures for an unpaired spin on a network where the substituent site group symmetry is not compatible with the perimeter. A deeper understanding is provided by the properties of the Kohn-Sham orbitals. The calculations of the X-doped GNDs reveal limitations in the use of the hex-radical hypothesis of the parent ground state to systems where foreign atoms lower symmetry and perturb the π- and σ-bond manifolds.

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U2 - 10.1063/1.4742193

DO - 10.1063/1.4742193

M3 - Article

AN - SCOPUS:84864863476

SN - 0021-9606

VL - 137

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 5

M1 - 054715

ER -