Relativistic Effects and Spin¶

Spin polarization¶

By default Band calculations are spin-restricted. You can instruct Band to perform a spin-unrestricted via the Unrestricted key:

Unrestricted Yes/No

Unrestricted

Type: Bool
Default value: No
Description: Controls whether Band should perform a spin-unrestricted calculation. Spin-unrestricted calculations are computationally roughly twice as expensive as spin-restricted.

The orbitals are occupied according to the aufbau principle.

If you want to enforce a specific spin-polarization (instead of occupying according to the aufbau principle) you can use the EnforcedSpinPolarization key:

EnforcedSpinPolarization float

EnforcedSpinPolarization

Type: Float
GUI name: Spin polarization
Description: Enforce a specific spin-polarization instead of occupying according to the aufbau principle. The spin-polarization is the difference between the number of alpha and beta electron. Thus, a value of 1 means that there is one more alpha electron than beta electrons. The number may be anything, including zero, which may be of interest when searching for a spin-flipped pair, that may otherwise end up in the (more stable) parallel solution.

Relativistic Effects¶

Relativistic effects are treated with the accurate and efficient ZORA approach 1 2, controlled by the Relativity keyword. Relativistic effects are negligible for light atoms, but grow to dramatic changes for heavy elements. A rule of thumb is: Relativistic effects are quite small for elements of row 4, but very large for row 6 elements (and later).

Relativity
   Level [None | Scalar | Spin-Orbit]
End

Relativity

Type: Block
Description: Options for relativistic effects.

Level

Type: Multiple Choice
Default value: Scalar
Options: [None, Scalar, Spin-Orbit]
GUI name: Relativity (ZORA)
Description: None: No relativistic effects. Scalar: Scalar relativistic ZORA. This option comes at very little cost. SpinOrbit: Spin-orbit coupled ZORA. This is the best level of theory, but it is (4-8 times) more expensive than a normal calculation. Spin-orbit effects are generally quite small, unless there are very heavy atoms in your system, especially with p valence electrons (like Pb). See also the SpinOrbitMagnetization key.

See also the SpinOrbitMagnetization key.

References

1: P.H.T. Philipsen, E. van Lenthe, J.G. Snijders and E.J. Baerends, Relativistic calculations on the adsorption of CO on the (111) surfaces of Ni, Pd, and Pt within the zeroth-order regular approximation. Physical Review B 56, 13556 (1997).
2: P.H.T. Philipsen, and E.J. Baerends, Relativistic calculations to assess the ability of the generalized gradient approximation to reproduce trends in cohesive properties of solids. Physical Review B 61, 1773 (2000).