Abstract
A viable strategy is developed for the general variational calculation of excited state wavefunctions which are constrained to remainorthogonal to all the lower-lying states of the samesymmetry. A key element of the strategy is to employ the penalised functional procedure for enforcing the relevant orthogonality constraints and the method of steepest descent to locate the constrained minima with respect to all variables, linear as well as nonlinear. The workability of the algorithm is tested by applying the technique for the optimization of nonlinear parameters in trial functions for the 2s state of H atom and singlet 1s2s states of helium atom and some isoelectronic ions.
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Dutta, P., Bhattacharyya, S.P. Orthogonality constrained general variational calculation of excited state wavefunctions and energies: A new strategy. Pramana - J Phys 34, 13–21 (1990). https://doi.org/10.1007/BF02846105
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DOI: https://doi.org/10.1007/BF02846105
Keywords
- Constrained variation
- variational calculation of excited states
- orthogonality constrained variation
- penalised functional method