Configuration Interaction for the Helium Isoelectronic Series

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Configuration interaction (CI) provides a systematic method for improving on single-configuration Hartree–Fock (HF) computations [1, 2]. This Demonstration considers the two-electron atoms in the helium isoelectronic series. The HF wavefunction is the optimal product of one-electron orbitals approximating the ground-state configuration. An improved representation of the ground state can be obtained by a superposition containing excited electronic configurations, including , , , …, with relative contributions determined by the variational principle.

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Shull and Löwdin [3] represented the total wavefunction in the form

,

where is the angle between and , while is the Legendre polynomial of degree . Note that the functions contain internal angular dependence but can still represent atomic states, such as and , with . In the computations presented in this Demonstration, we consider only the , , and contributions to CI. The contribution is taken as the HF function , which can be very closely approximated using double-zeta orbitals

.

The contribution is represented by the orthogonalized Slater-type function

.

Together, these two contributions can closely approximate the -limit to the CI function, as defined by Shull and Löwdin. The and contributions are represented using simple Slater-type orbitals:

and

,

with

for and

for .

All the relevant matrix elements of the Hamiltonian are then computed; for example,

,

,

and so forth. All energies are expressed in Hartree atomic units: .

Plots of the radial distribution function for each component configuration are also shown on the left. The relative magnitudes are not to scale.

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Contributed by: S. M. Blinder (February 2018)
Open content licensed under CC BY-NC-SA


Snapshots


Details

Snapshot 1: the single-configuration Hartree–Fock result

Snapshot 2: approximation to the -limit; a more accurate computation gives hartrees

Snapshot 3: result using optimized parameters; reaching is considered a milestone

References

[1] S. M. Blinder, "The Hartree–Fock Approximation," Mathematical Physics in Theoretical Chemistry (S. M. Blinder and J. E. House, eds.), Amsterdam: Elsevier, forthcoming.

[2] Wikipedia. "Configuration Interaction." (Feb 14, 2018) en.wikipedia.org/wiki/Configuration_interaction.

[3] H. Shull and P.-O. Löwdin, "Superposition of Configurations and Natural Spin Orbitals: Applications to the He Problem," Journal of Chemical Physics, 30(3), 1959 pp. 617–626. doi:10.1063/1.1730019.



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