Orbital rotations

Orbital rotations#

Reference state parameterization#

In time-dependent Hartree–Fock, the variations of orbitals in the time-independent reference state, \(| 0 \rangle = | \Psi_\mathrm{HF} \rangle\), can be introduced by means of an exponential parameterization

\[ | \bar{\Psi}(t) \rangle = e^{-i\hat{\kappa}(t)} | 0 \rangle \]

where

\[ \hat{\kappa}(t) = \sum_{a}^\mathrm{virt} \sum_{i}^\mathrm{occ} \Big[ \kappa_{ai}(t) \, \hat{a}^{\dagger}_a \hat{a}_i + \kappa_{ai}^*(t) \, \hat{a}^{\dagger}_i \hat{a}_a \Big] \]

It is convenient to organize the electron transfer amplitudes into the virtual–occupied (vo) and occupied–virtual (ov) blocks of a molecular orbital (MO) matrix. In the vo- and ov-blocks, we put amplitudes \(\kappa_{ai}\) and \(\kappa_{ai}^\ast \equiv \kappa_{ia}\), respectively.

\[\begin{split} \boldsymbol{\kappa} = \begin{bmatrix} 0 & \kappa_{ia} \\ \kappa_{ai} & 0 \\ \end{bmatrix} \end{split}\]

The \(\kappa\)-matrix is Hermitian and so is the \(\hat{\kappa}\)-operator.

Generator of orbital rotations#

For an \(N\)-electron system, we have

\[ | 0 \rangle = \prod_{i=1}^N \hat{a}^{\dagger}_i | \mathrm{vac} \rangle \]

Since

\[ e^{i\hat{\kappa}}|\mathrm{vac}\rangle = \left(1+i\hat{\kappa}-\frac{1}{2}\hat{\kappa}^2+\ldots\right)|\mathrm{vac}\rangle = |\mathrm{vac}\rangle \]

we have

\[\begin{align*} | \bar{\Psi}(t) \rangle & = e^{-i\hat{\kappa}}\hat{a}^{\dagger}_1e^{i\hat{\kappa}}e^{-i\hat{\kappa}}\hat{a}^{\dagger}_2e^{i\hat{\kappa}}\ldots e^{-i\hat{\kappa}}\hat{a}^{\dagger}_Ne^{i\hat{\kappa}}|\mathrm{vac}\rangle \\ & = \hat{\tilde{a}}^{\dagger}_1\hat{\tilde{a}}^{\dagger}_2 \ldots \hat{\tilde{a}}^{\dagger}_N |\mathrm{vac}\rangle , \end{align*}\]

where we have introduced time-transformed creation operators

\[ \hat{\tilde{a}}^{\dagger}_p = e^{-i\hat{\kappa}}\hat{a}^{\dagger}_pe^{i\hat{\kappa}} = \hat{a}^{\dagger}_p -i\left[\hat{\kappa},\hat{a}^{\dagger}_p\right] -\frac{1}{2}\left[\hat{\kappa},\left[\hat{\kappa},\hat{a}^{\dagger}_p\right]\right]+\ldots \]

From the algebra of creation and annihilation operators, we find that

\[ \left[\hat{\kappa},\hat{a}^{\dagger}_p\right]=\hat{a}^{\dagger}_r\kappa_{rp} \]

and therefore

\[ \hat{\tilde{a}}^{\dagger}_p = \hat{a}^{\dagger}_{r}\left(\delta_{rp}-i\kappa_{rp}-\frac{1}{2}\kappa^2_{rp}+\ldots\right) = \hat{a}^{\dagger}_{r} \, U_{rp} \]

where we have introduced the unitary matrix

\[ \mathbf{U} = e^{-i\boldsymbol{\kappa}} \]

Following the determinant property of linearity, this transformation of creation operators translates directly into a transformation of orbitals in the wave function

\[ | \bar{\Psi}(t) \rangle = | \tilde{\psi}_1, \tilde{\psi}_2, \ldots, \tilde{\psi}_N \rangle \]

where

\[ \tilde{\psi}_p(\mathbf{r}) = \psi_r(\mathbf{r}) \, U_{rp} \]

This transformation preserves orthonormality among the orbitals and the \(\hat{\kappa}\)-operator can be thought of as a generator of rotations in the space of molecular orbitals.

Phase isolation#

The phase is preserved in the orbital transformation in the sense that the overall phase of the reference state does not change, or in terms of orbitals

\[ \langle \psi_p | \tilde{\psi}_p \rangle \in {\cal R} \]

It can therefore be used for the parameterization of phase-isolated wave functions as indicated with the overbar in \(| \bar{\Psi}(t) \rangle\).

Spin symmetry#

If we wish to preserve the singlet spin symmetry of a closed-shell reference state, we use spin-adapted electron-transfer operators

\[ \hat{\kappa}(t) = \sum_{a}^\mathrm{virt} \sum_{i}^\mathrm{occ} \Big[ \kappa_{ai}(t) \, \hat{E}^{\dagger}_{ai} + \kappa_{ai}^*(t) \, \hat{E}^{\dagger}_{ia} \Big] \]

where

\[ \hat{E}_{pq}^\dagger = \hat{a}^\dagger_{p\alpha} \hat{a}_{q\alpha} + \hat{a}^\dagger_{p\beta} \hat{a}_{q\beta} \]

Summations here run over molecular orbitals (MOs) instead of spin orbitals, and consequently, the number of parameters is reduced by a factor of four.

We get

\[ | \bar{\Psi}(t) \rangle = | \tilde{\psi}_1, \tilde{\psi}_\bar{1}, \ldots, \tilde{\psi}_{N/2}, \tilde{\psi}_\overline{N/2} \rangle \]

where

\[\begin{split} \tilde{\psi}_p(\mathbf{r}) = \tilde{\phi}_p(\mathbf{r}) \begin{pmatrix} 1 \\ 0 \end{pmatrix} ; \qquad \tilde{\psi}_\bar{p}(\mathbf{r}) = \tilde{\phi}_p(\mathbf{r}) \begin{pmatrix} 0 \\ 1 \end{pmatrix} \end{split}\]

with

\[ \tilde{\phi}_p(\mathbf{r}) = \phi_r(\mathbf{r}) \, \big[e^{-i \kappa}\big]_{rp} \]

Illustrations#

import numpy as np
from scipy.linalg import expm

Let us consider a system of two-electrons in two MOs (or four spin orbitals).

../../_images/determinant-wide.svg

Multi-electron excited determinants#

The generator of rotations includes only single electron excitation operators but the range of the transformation includes all determinants, also multi-electron excited determinants.

We reach the doubly excited determinant with

\[\begin{split} \boldsymbol{\kappa} = \begin{bmatrix} 0 & 0 & -i\pi/2 & 0 \\ 0 & 0 & 0 & -i\pi/2 \\ i\pi/2 & 0 & 0 & 0 \\ 0 & i\pi/2 & 0 & 0 \\ \end{bmatrix} \end{split}\]
k31, k32, k41, k42 = (np.pi * 0.5j, 0, 0, np.pi * 0.5j)
k13, k23, k14, k24 = np.conjugate((k31, k32, k41, k42))

kappa = np.array(
    [[0, 0, k13, k14], [0, 0, k23, k24], [k31, k32, 0, 0], [k41, k42, 0, 0]]
)

U = expm(-1j * kappa)
print("Occupied orbitals:\n", U.real[:, :2])

Occupied orbitals:
 [[0. 0.]
 [0. 0.]
 [1. 0.]
 [0. 1.]]

Phase isolation#

Let us create a random generator of orbital rotations on the form

\[\begin{split} \boldsymbol{\kappa} = \begin{bmatrix} 0 & \kappa_{ia} \\ \kappa_{ai} & 0 \\ \end{bmatrix} \end{split}\]
np.set_printoptions(precision=6, suppress=True, linewidth=170)
np.random.seed(20240208)

kappa = np.zeros((4, 4), dtype=complex)
kappa[2:, :2] = np.random.rand(2, 2) + 1j * np.random.rand(2, 2)
kappa = kappa + np.conjugate(kappa).T

The transformed orbitals become

U = expm(-1j * kappa)
print("Transformed orbitals:\n", U)

Transformed orbitals:
 [[ 0.414314+0.j       -0.272098-0.000049j -0.063249-0.357053j -0.609038-0.501889j]
 [-0.272098+0.000049j  0.784682+0.j       -0.400653-0.136519j -0.138307-0.334586j]
 [ 0.063249-0.357053j  0.400653-0.136519j  0.78434 +0.j       -0.265899+0.058835j]
 [ 0.609038-0.501889j  0.138307-0.334586j -0.265899-0.058835j  0.414656+0.j      ]]

We note that the diagonal elements are real, i.e.

\[ \langle \psi_p | \tilde{\psi}_p \rangle \in {\cal R} \]

Spin symmetry#

The singlet spin symmetry of the closed-shell reference state, \(|\psi_1, \psi_2 \rangle\), is preserved by requiring that \(\kappa_{42} = \kappa_{31}\) and \(\kappa_{41} = \kappa_{32} = 0\).

As an example, let us consider

\[\begin{split} \boldsymbol{\kappa} = \begin{bmatrix} 0 & 0 & -i\pi/4 & 0 \\ 0 & 0 & 0 & -i\pi/4 \\ i\pi/4 & 0 & 0 & 0 \\ 0 & i\pi/4 & 0 & 0 \\ \end{bmatrix} \end{split}\]
k31, k32, k41, k42 = (np.pi * 0.25j, 0, 0, np.pi * 0.25j)
k13, k23, k14, k24 = np.conjugate((k31, 0, 0, k42))

kappa = np.array(
    [[0, 0, k13, k14], [0, 0, k23, k24], [k31, k32, 0, 0], [k41, k42, 0, 0]]
)

U = expm(-1j * kappa)
print("Occupied orbitals:\n", U.real[:, :2])

Occupied orbitals:
 [[0.707107 0.      ]
 [0.       0.707107]
 [0.707107 0.      ]
 [0.       0.707107]]

The resulting state can be written

\[\begin{align*} | \bar{\Psi} \rangle & = | \tilde{\psi_1}, \tilde{\psi_2} \rangle = | (\psi_1 + \psi_3)/\sqrt{2}, (\psi_2 + \psi_4)/\sqrt{2} \rangle \\ & = \frac{1}{2} \Big[ | \psi_1, \psi_2 \rangle + | \psi_1, \psi_4 \rangle + | \psi_3, \psi_2 \rangle + | \psi_3, \psi_4 \rangle \Big] \end{align*}\]

where we identify the reference state and the doubly excited determinant alongside the singly excited spin-adapted configuration of singlet spin symmetry.

Finally, let us consider a somewhat larger system with four electrons in six MOs (or 12 spin orbitals). In the spin-orbital basis, it is convenient to organize parameters in spin blocks.

\[\begin{split} \boldsymbol{\kappa} = \begin{bmatrix} 0 & 0 & \kappa_{ia} & \kappa_{i\bar{a}} \\ 0 & 0 & \kappa_{\bar{i}a} & \kappa_{\bar{i}\bar{a}} \\ \kappa_{ai} & \kappa_{a\bar{i}} & 0 & 0\\ \kappa_{\bar{a}i} & \kappa_{\bar{a}\bar{i}} & 0 & 0\\ \end{bmatrix} \end{split}\]

Let us perform a random transformation of the spin orbitals and print out \(\tilde{\psi}_1\) and \(\tilde{\psi}_\bar{1}\) as examples.

k31, k41, k51, k61, k32, k42, k52, k62 = np.random.rand(8) + 1j * np.random.rand(8)
k13, k14, k15, k16, k23, k24, k25, k26 = np.conjugate(
    (k31, k41, k51, k61, k32, k42, k52, k62)
)

kappa = np.array(
    [
        [0, 0, 0, 0, k13, k14, k15, k16, 0, 0, 0, 0],
        [0, 0, 0, 0, k23, k24, k25, k26, 0, 0, 0, 0],
        [0, 0, 0, 0, 0, 0, 0, 0, k13, k14, k15, k16],
        [0, 0, 0, 0, 0, 0, 0, 0, k23, k24, k25, k26],
        [k31, k32, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0],
        [k41, k42, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0],
        [k51, k52, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0],
        [k61, k62, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0],
        [0, 0, k31, k32, 0, 0, 0, 0, 0, 0, 0, 0],
        [0, 0, k41, k42, 0, 0, 0, 0, 0, 0, 0, 0],
        [0, 0, k51, k52, 0, 0, 0, 0, 0, 0, 0, 0],
        [0, 0, k61, k62, 0, 0, 0, 0, 0, 0, 0, 0],
    ]
)

U = expm(-1j * kappa)
print("Lowest occupied alpha-spin orbital:\n", U[:,0])
print("Lowest occupied beta-spin orbital:\n", U[:,2])

Lowest occupied alpha-spin orbital:
 [ 0.195145-0.j       -0.674738-0.007566j  0.      +0.j        0.      +0.j        0.272185-0.364692j  0.150157-0.219078j -0.077445-0.261337j  0.390656+0.045347j
  0.      +0.j        0.      +0.j        0.      +0.j        0.      +0.j      ]
Lowest occupied beta-spin orbital:
 [ 0.      +0.j        0.      +0.j        0.195145-0.j       -0.674738-0.007566j  0.      +0.j        0.      +0.j        0.      +0.j        0.      +0.j
  0.272185-0.364692j  0.150157-0.219078j -0.077445-0.261337j  0.390656+0.045347j]

We note that the spatial parts of the two spin orbitals are identical.

If we instead implement the transformation in the MO-basis, the dimension of the \(\kappa\)-matrix becomes reduced by a factor of two.

kappa = np.array(
    [
        [0, 0, k13, k14, k15, k16],
        [0, 0, k23, k24, k25, k26],
        [k31, k32, 0, 0, 0, 0],
        [k41, k42, 0, 0, 0, 0],
        [k51, k52, 0, 0, 0, 0],
        [k61, k62, 0, 0, 0, 0],
    ]
)

U = expm(-1j * kappa)
print("Lowest occupied molecular orbital:\n", U[:,0])

Lowest occupied molecular orbital:
 [ 0.195145-0.j       -0.674738-0.007566j  0.272185-0.364692j  0.150157-0.219078j -0.077445-0.261337j  0.390656+0.045347j]

We note that this molecular orbital is identical to the spatial parts of the spin orbitals in the previous example.

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