The self-consistent nonorthogonal group function approach in reduced basis frozen-core calculations

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Abstract

The orthogonal group function approach, as based on the Huzinaga equation, is extensively applied in reduced basis frozen-core calculations. Although the theory is developed for orthogonal electronic groups, the use of reduced basis sets prevents strict orthogonality and the formalism is complemented to take, partially, into account nonorthogonality (projection factors, projection energy). In the present article, an alternative to this approach, based on the nonorthogonal formalism, is proposed. An orbital equation is derived from the Adams-Gilbert equation and the energy is evaluated according to a recent proposal based on the power-series expansion of the overlap energy. A comparative overview of the orthogonal and nonorthogonal formalisms is presented and the results of reduced basis frozen-core calculations as obtained with the two methods are compared. It is found that the nonorthogonal formulation predicts equilibrium geometrical parameters in some cases similarly and, in other cases, slightly better than does the orthogonal one. Based on this observation and on the fact that the nonorthogonal formulation is exempt from empirical parameters (projection factors), it is concluded that the nonorthogonal formalism represents an appealing alternative in reduced basis frozen-core calculations.

Original languageEnglish
Pages (from-to)361-367
Number of pages7
JournalInternational Journal of Quantum Chemistry
Volume57
Issue number3
Publication statusPublished - 1996

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projection
formalism
formulations
orthogonality
power series
series expansion
energy
proposals
orbitals
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "The self-consistent nonorthogonal group function approach in reduced basis frozen-core calculations",
abstract = "The orthogonal group function approach, as based on the Huzinaga equation, is extensively applied in reduced basis frozen-core calculations. Although the theory is developed for orthogonal electronic groups, the use of reduced basis sets prevents strict orthogonality and the formalism is complemented to take, partially, into account nonorthogonality (projection factors, projection energy). In the present article, an alternative to this approach, based on the nonorthogonal formalism, is proposed. An orbital equation is derived from the Adams-Gilbert equation and the energy is evaluated according to a recent proposal based on the power-series expansion of the overlap energy. A comparative overview of the orthogonal and nonorthogonal formalisms is presented and the results of reduced basis frozen-core calculations as obtained with the two methods are compared. It is found that the nonorthogonal formulation predicts equilibrium geometrical parameters in some cases similarly and, in other cases, slightly better than does the orthogonal one. Based on this observation and on the fact that the nonorthogonal formulation is exempt from empirical parameters (projection factors), it is concluded that the nonorthogonal formalism represents an appealing alternative in reduced basis frozen-core calculations.",
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T1 - The self-consistent nonorthogonal group function approach in reduced basis frozen-core calculations

AU - Ferenczy, G.

PY - 1996

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N2 - The orthogonal group function approach, as based on the Huzinaga equation, is extensively applied in reduced basis frozen-core calculations. Although the theory is developed for orthogonal electronic groups, the use of reduced basis sets prevents strict orthogonality and the formalism is complemented to take, partially, into account nonorthogonality (projection factors, projection energy). In the present article, an alternative to this approach, based on the nonorthogonal formalism, is proposed. An orbital equation is derived from the Adams-Gilbert equation and the energy is evaluated according to a recent proposal based on the power-series expansion of the overlap energy. A comparative overview of the orthogonal and nonorthogonal formalisms is presented and the results of reduced basis frozen-core calculations as obtained with the two methods are compared. It is found that the nonorthogonal formulation predicts equilibrium geometrical parameters in some cases similarly and, in other cases, slightly better than does the orthogonal one. Based on this observation and on the fact that the nonorthogonal formulation is exempt from empirical parameters (projection factors), it is concluded that the nonorthogonal formalism represents an appealing alternative in reduced basis frozen-core calculations.

AB - The orthogonal group function approach, as based on the Huzinaga equation, is extensively applied in reduced basis frozen-core calculations. Although the theory is developed for orthogonal electronic groups, the use of reduced basis sets prevents strict orthogonality and the formalism is complemented to take, partially, into account nonorthogonality (projection factors, projection energy). In the present article, an alternative to this approach, based on the nonorthogonal formalism, is proposed. An orbital equation is derived from the Adams-Gilbert equation and the energy is evaluated according to a recent proposal based on the power-series expansion of the overlap energy. A comparative overview of the orthogonal and nonorthogonal formalisms is presented and the results of reduced basis frozen-core calculations as obtained with the two methods are compared. It is found that the nonorthogonal formulation predicts equilibrium geometrical parameters in some cases similarly and, in other cases, slightly better than does the orthogonal one. Based on this observation and on the fact that the nonorthogonal formulation is exempt from empirical parameters (projection factors), it is concluded that the nonorthogonal formalism represents an appealing alternative in reduced basis frozen-core calculations.

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