Instabilities of the symmetry-adapted restricted-hartree–fock ground state in infinite polyenes. I. Singlet instabilities

P. Karadakov; O. Castaño

doi:10.1002/qua.560220212

Instabilities of the symmetry-adapted restricted-hartree–fock ground state in infinite polyenes. I. Singlet instabilities

P. Karadakov, O. Castaño

Chemistry

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Abstract

The singlet instabilities of the RHF ground state in infinite polyenes have been studied in the framework of a semiempirical PPP Hamiltonian, accounting for long-range Coulomb interactions until convergence of the ground-state energy per electron value. The symmetry-adapted RHF solution (SAS) has been shown to be unstable to the formation of bond-order alternation waves (BAW's) and charge-density waves (CDW's). The CDW solutions have been shown to be higher in energy than the corresponding BAW solutions and to represent saddle points of the energy hypersurface, unstable to the formation of BAW's for physically realistic range of variation of the semiempirical parameters. Analytical formulas for the SAS ground-state energy per electron have been derived in case of a Coulomb law and a Mataga–Nishimoto formula for the two-center Coulomb integrals.

Original language	Undefined/Unknown
Pages (from-to)	351-365
Number of pages	15
Journal	INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
Volume	22
Issue number	2
DOIs	https://doi.org/10.1002/qua.560220212
Publication status	Published - 1982

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http://dx.doi.org/10.1002/qua.560220212

Cite this

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title = "Instabilities of the symmetry-adapted restricted-hartree–fock ground state in infinite polyenes. I. Singlet instabilities",

abstract = "The singlet instabilities of the RHF ground state in infinite polyenes have been studied in the framework of a semiempirical PPP Hamiltonian, accounting for long-range Coulomb interactions until convergence of the ground-state energy per electron value. The symmetry-adapted RHF solution (SAS) has been shown to be unstable to the formation of bond-order alternation waves (BAW's) and charge-density waves (CDW's). The CDW solutions have been shown to be higher in energy than the corresponding BAW solutions and to represent saddle points of the energy hypersurface, unstable to the formation of BAW's for physically realistic range of variation of the semiempirical parameters. Analytical formulas for the SAS ground-state energy per electron have been derived in case of a Coulomb law and a Mataga–Nishimoto formula for the two-center Coulomb integrals.",

author = "P. Karadakov and O. Casta{\~n}o",

year = "1982",

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pages = "351--365",

journal = "INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY",

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T1 - Instabilities of the symmetry-adapted restricted-hartree–fock ground state in infinite polyenes. I. Singlet instabilities

AU - Karadakov, P.

AU - Castaño, O.

PY - 1982

Y1 - 1982

N2 - The singlet instabilities of the RHF ground state in infinite polyenes have been studied in the framework of a semiempirical PPP Hamiltonian, accounting for long-range Coulomb interactions until convergence of the ground-state energy per electron value. The symmetry-adapted RHF solution (SAS) has been shown to be unstable to the formation of bond-order alternation waves (BAW's) and charge-density waves (CDW's). The CDW solutions have been shown to be higher in energy than the corresponding BAW solutions and to represent saddle points of the energy hypersurface, unstable to the formation of BAW's for physically realistic range of variation of the semiempirical parameters. Analytical formulas for the SAS ground-state energy per electron have been derived in case of a Coulomb law and a Mataga–Nishimoto formula for the two-center Coulomb integrals.

AB - The singlet instabilities of the RHF ground state in infinite polyenes have been studied in the framework of a semiempirical PPP Hamiltonian, accounting for long-range Coulomb interactions until convergence of the ground-state energy per electron value. The symmetry-adapted RHF solution (SAS) has been shown to be unstable to the formation of bond-order alternation waves (BAW's) and charge-density waves (CDW's). The CDW solutions have been shown to be higher in energy than the corresponding BAW solutions and to represent saddle points of the energy hypersurface, unstable to the formation of BAW's for physically realistic range of variation of the semiempirical parameters. Analytical formulas for the SAS ground-state energy per electron have been derived in case of a Coulomb law and a Mataga–Nishimoto formula for the two-center Coulomb integrals.

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DO - 10.1002/qua.560220212

M3 - Article

SN - 1097-461X

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