theochem / ModelHamiltonian

Generate 1- and 2-electron integrals so that molecular quantum chemistry software can be used for model Hamiltonians.
https://modelh.qcdevs.org
GNU Lesser General Public License v3.0
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Alternative Spin Representation #144

Open PaulWAyers opened 3 weeks ago

PaulWAyers commented 3 weeks ago

Right now we use a spin representation where we map spins onto electron pairs. This is convenient since it maps spin-models onto seniority-zero Hamiltonians/wavefunctions. It is not convenient in the sense that the $\hat{S}_x$ and $\hat{S}_y$ operators break particle-number symmetry, so a general XYZ Heisenberg model is inaccessible.

There is an alternative approach. We can directly model the spin on each orbital as $Sk^+ = a{k\alpha}^\dagger a_{k\beta}$ converting a down-spin electron in spatial orbital $k$ to an up-spin electron in spatial orbital $k$ and annhilating the wavefunction if the orbital is empty or has a up-spin electron already in it. Similarly, $Sk^- = a{k\beta}^\dagger a_{k\alpha}$ changes an up-spin electron in orbital $k$ to a down-spin electron, and otherwise gives zero. $S^Zk=\tfrac{1}{2}\left(a{k\alpha}^\dagger a{k\alpha}-a{k\beta}^\dagger a_{k\beta} \right)$ gives $\pm \tfrac{1}{2}$ depending on whether the $k$-th orbital has a spin-up or spin-down electron.

This is a legitimate representation of the spin algebra because

$$ [S_k^+ , Sl^-] = 2\delta{kl} S_k^Z $$

$$ [S_k^Z, Sl^{\pm}] = \pm \delta{kl} S_k^{\pm} $$

The interesting state then is the maximum seniority state where every spatial orbital is singly-occupied. However, it seems that now a fully general XYZ model is allowable, because terms like $S_k^+ \pm Sl^-$ are now allowed. The key symmetry to maintain now is the maximum-seniority-sector, noting that we need to keep track of cases with different numbers of $N\alpha$ and $N_{\beta}$ electrons (so when it comes time to solve the Schrödinger equation, it may be easiest to support this in the generalized framework).