*Code author: Justin M. Turney, Robert M. Parrish, and Andrew C. Simmonett*

*Section author: Robert M. Parrish*

*Module:* *Keywords*, *PSI Variables*, LIBSCF_SOLVER, LIBMINTS, LIBFOCK, LIBDIIS

Self-Consistent-Field (SCF) theory forms the cornerstone of *ab initio* quantum
chemistry. Here SCF refers both to conventional Hartree–Fock (HF) molecular
orbital theory and also to generalized Kohn–Sham Density Functional Theory
(KS-DFT). PSI4 contains a wholly rewritten SCF code, including many of the
most popular spin specializations, several efficient numerical methods for
treating Fock Matrix construction, and a brand new KS-DFT code featuring many of
the most popular DFT functional technologies.

An illustrative example of using the SCF module is as follows:

```
molecule {
0 3
O
O 1 1.21
}
set {
basis cc-pvdz
guess sad
reference uhf
scf_type pk
}
energy('scf')
```

This will run a UHF computation for triplet molecular oxygen (the ground state) using a PK algorithm for the Electron Repulsion Integrals (ERI) and starting from a Superposition of Atomic Densities (SAD) guess. DF integrals are automatically used to converge the DF-SCF solution before the PK algorithm is activated. After printing all manner of titles, geometries, sizings, and algorithm choices, the SCF finally reaches the iterations:

```
Total Energy Delta E RMS |[F,P]|
@UHF iter 0: -149.76816019169962 -1.49768e+02 1.36000e-01
@UHF iter 1: -149.59759112756984 1.70569e-01 2.42437e-02
@UHF iter 2: -149.62372414554761 -2.61330e-02 6.10239e-03 DIIS
@UHF iter 3: -149.62643112722810 -2.70698e-03 2.17299e-03 DIIS
@UHF iter 4: -149.62690062294968 -4.69496e-04 5.66895e-04 DIIS
@UHF iter 5: -149.62694151409750 -4.08911e-05 1.26359e-04 DIIS
@UHF iter 6: -149.62694337042228 -1.85632e-06 1.84114e-05 DIIS
@UHF iter 7: -149.62694340901407 -3.85918e-08 2.91692e-06 DIIS
@UHF iter 8: -149.62694340999002 -9.75945e-10 3.11857e-07 DIIS
DF guess converged.
...
@UHF iter 9: -149.62730705470665 -3.63645e-04 8.63718e-05 DIIS
@UHF iter 10: -149.62730737347948 -3.18773e-07 1.50227e-05 DIIS
@UHF iter 11: -149.62730738537107 -1.18916e-08 3.80497e-06 DIIS
@UHF iter 12: -149.62730738624032 -8.69250e-10 7.06690e-07 DIIS
```

The first set of iterations are from the DF portion of the computation, the second set use the exact (but much slower) PK algorithm. Within the DF portion of the computation, the zeroth-iteration uses a non-idempotent density matrix obtained from the SAD guess, so the energy is unphysically low. However, the first true iteration is quite close to the final DF energy, highlighting the efficiency of the SAD guess. Pulay’s DIIS procedure is then used to accelerate SCF convergence, with the DF phase reaching convergence in eight true iterations. When used together, SAD and DIIS are usually sufficient to converge the SCF for all but the most difficult systems. Additional convergence techniques are available for more difficult cases, and are detailed below. At this point, the code switches on the requested PK integrals technology, which requires only four full iterations to reach convergence, starting from the DF guess. This hybrid DF/conventional procedure can significantly accelerate SCF computations requiring exact integrals, especially when used in concert with the integral-direct conventional algorithm.

After the iterations are completed, a number of one-electron properties are
printed, and some bookkeeping is performed to set up possible correlated
computations. Additional one-electron properties are available by increasing the
*PRINT* option. Also printed are the occupied and virtual orbital energies,
which are useful in elucidating the stability and reactivity of the system.

The objective of Hartree-Fock (HF) Theory is to produce the optimized Molecular Orbitals (MOs) ,

Here, are the basis functions, which, in PSI4 are contracted cartesian Gaussian functions often referred to as Atomic Orbitals (AOs). The matrix contains the MO coefficients, which are the constrained variational parameters in Hartree-Fock. The molecular orbitals, are used to build the simplest possible antisymmetric wavefunction, a single Slater determinant,

This form for the Hartree-Fock wavefunction is actually entirely equivalent to treating the electron correlation as a mean field repulsion in instead of a more complicated effect in .

Considering the electronic Hamiltonian,

the Hartree-Fock energy is, by Slater’s rules,

Here is the AO-basis one-electron potential, encapsulating both electron-nuclear attraction and kinetic energy,

is the AO-basis density matrix, build from the occupied orbital coefficients,

and is the Fock matrix, which is the effective one-body potential at the current value of the density,

Here the tensor is an AO Electron-Repulsion Integral (ERI) in chemists’ notation,

The MO coefficients are found as the generalized eigenvectors of the Fock Matrix,

The eigenvalues are the orbital energies, and the metric matrix is the AO-basis overlap matrix

Note that the Fock Matrix depends on the density (both alpha and beta), and therefore the orbitals. Because of this, SCF is a nonlinear procedure, which terminates when the generating orbitals are self-consistent with the Fock matrix they generate.

The formation of the Coulomb matrix and the exchange matrix dominate the computational effort of the SCF procedure. For very large systems, diagonalization of the Fock matrix can also present a significant hurdle.

Minimal input for a Hartree-Fock computation is a molecule block, basis set
option, and a call to `energy('scf')`:

```
molecule {
He
}
set basis sto-3g
energy('scf')
```

This will run a Restricted Hartree-Fock (RHF) on neutral singlet Helium in
spatial symmetry with a minimal `STO-3G` basis, 1.0E-6
energy and 1.0E-5 density convergence criteria (since single-point, see
*SCF Convergence & Algorithm*), a DF ERI algorithm, symmetric
orthogonalization, DIIS, and a core Hamiltonian guess. For more
information on any of these options, see the relevant section below.

PSI4 implements the most popular spin specializations of Hartree-Fock theory, including:

- Restricted Hartree-Fock (RHF) [Default]
- Appropriate only for closed-shell singlet systems, but twice as efficient as the other flavors, as the alpha and beta densities are constrained to be identical.
- Unrestricted Hartree-Fock (UHF)
- Appropriate for most open-shell systems, and fairly easy to converge. The spatial parts of the alpha and beta orbitals are fully independent of each other, which allows a considerable amount of flexibility in the wavefunction. However, this flexibility comes at the cost of spin symmetry; UHF wavefunctions need not be eigenfunctions of the operator. The deviation of this operator from its expectation value is printed on the output file. If the deviation is greater than a few hundredths, it is advisable to switch to an ROHF to avoid this “spin-contamination” problem.
- Restricted Open-Shell Hartree-Fock (ROHF)
- Appropriate for open-shell systems where spin-contamination is problem. Sometimes more difficult to converge, and assumes uniformly positive spin polarization (the alpha and beta doubly-occupied orbitals are identical).
- Constrained Unrestricted Hartree-Fock (CUHF)
- A variant of ROHF that starts from a UHF ansatz, and is therefore often easier to converge.

These can be invoked by the *REFERENCE* keyword, which defaults to `RHF`.
The charge and multiplicity may either be specified in the molecule definition:

```
molecule h {
0 2 # Neutral doublet
H
}
```

or, dynamically, by setting the relevant attributes in the Python molecule object:

```
h.set_molecular_charge(0)
h.set_multiplicity(2)
```

Abelian spatial symmetry is fully supported in PSI4, and can be used to
obtain physical interpretation of the molecular orbitals, to assist in difficult
convergence cases, and, in some methods, to obtain significant performance
gains. The point group of the molecule is inferred when reading the molecule
section, and may be overridden by the `symmetry` flag, as in:

```
molecule h {
0 2
H
symmetry c1
}
```

or by the `set_point_group` Python molecule attribute:

```
h.set_point_group('c2v')
```

During the SCF procedure, the occupation of orbitals is typically determined by
the Aufbau principal across all spatial symmetries. This may result in the
occupation shifting between iterations. If the occupations are known *a priori*,
they may be clamped throughout the procedure by using the *DOCC* and
*SOCC* options. For instance, all good quantum chemists know that
water is
actually,:

```
molecule h2o {
0 1
O
H 1 1.0
H 1 1.0 2 104.5
}
set {
docc [3,0,1,1] # 1A1 2A1 1B1 3A1 1B2
basis cc-pvdz
}
energy('scf')
```

For certain problems, such diradicals, allowing the spin-up and spin-down orbitals to differ in closed-shell computations can be advantageous; this is known as symmetry breaking. The resulting wavefunction will often provide superior energetics, due to the increased flexibility, but will suffer non-physicical spin contamination from higher multiplicity states. PSI4 can compute a high-spin triplet wavefunction and then use this as a guess for the broken-symmetry low spin state. To do this, you request broken symmetry in the `energy()` call, using one of the following::

```
energy('uhf', brokensymmetry=True)
or, equivalently
set reference uhf
energy('scf', brokensymmetry=True)
```

One of the first steps in the SCF procedure is the determination of an
orthogonal basis (known as the OSO basis) from the atomic orbital basis (known
as the AO basis). The Molecular Orbital basis (MO basis) is then built as a
particular unitary transformation of the OSO basis. In PSI4, the
determination of the OSO basis is accomplished via either symmetric or canonical
orthogonalization. Symmetric orthogonalization uses the symmetric inverse square
root of the overlap matrix for the orthogonalization matrix. Use of symmetric
orthogonalization always yields the same number of OSO functions (and thereby
MOs) as AO functions. However, this may lead to numerical problems if the
overlap matrix has small eigenvalues, which may occur for large systems or for
systems where diffuse basis sets are used. This problem may be avoided by using
canonical orthogonalization, in which an asymmetric inverse square root of the
overlap matrix is formed, with numerical stability enhanced by the elimination
of eigenvectors corresponding to very small eigenvalues. As a few combinations
of AO basis functions may be discarded, the number of canonical-orthogonalized
OSOs and MOs may be slightly smaller than the number of AOs. In PSI4,
symmetric orthogonalization is used by default, unless the smallest overlap
eigenvalue falls below the user-supplied double option *S_TOLERANCE*, which
defaults to 1E-7. If the smallest eigenvalue is below this cutoff, canonical
orthogonalization is forced, and all eigenvectors corresponding to eigenvalues
below the cutoff are eliminated. Use of canonical orthogonalization can be
forced by setting the *S_ORTHOGONALIZATION* option to `CANONICAL`. Note
that in practice, the MOs and OSOs are built separately within each irrep from
the symmetry-adapted combinations of AOs known as Unique Symmetry Orbitals
(USOs). For canonical orthogonalization, this implies that the number of MOs
and OSOs per irrep may be slightly smaller than the number of USOs per irrep.

A contrived example demonstrating OSOs/MOs vs. AOs with symmetry is shown below:

```
molecule h2o {
0 1
O
H 1 1.0
H 1 1.0 2 104.5
symmetry c2 # Two irreps is easier to comprehend
}
set {
s_tolerance 0.0001 # Set an unreasonably tight
# tolerance to force canonical
basis aug-cc-pv5z # This diffuse basis will have
# small-ish eigenvalues for even H2O
}
energy('scf')
```

Output:

```
... Initialization ...
==> Pre-Iterations <==
Minimum eigenvalue in the overlap matrix is 1.6888059293E-05.
Using Canonical Orthogonalization with cutoff of 1.0000000000E-04.
Overall, 3 of 287 possible MOs eliminated.
... Initial Orbital Guess Information ...
-------------------------------------------------------
Irrep Nso Nmo Nalpha Nbeta Ndocc Nsocc
-------------------------------------------------------
A 145 144 3 3 3 0
B 142 140 2 2 2 0
-------------------------------------------------------
Total 287 284 5 5 5 0
-------------------------------------------------------
```

In this example, there are 287 AO basis functions after spherical harmonics are applied. These are used to produce 287 symmetry adapted USOs, 145 of which are assigned to irrep A, and 142 of which are assigned to irrep B. Within irrep A, 144 OSOs fall above the eigenvalue cutoff, and within irrep B 140 OSOs fall above the eigenvalue cutoff. In total, 284 molecular orbitals are chosen from 287 AOs/USOs. The table also shows the initial assignment of electrons to irreps.

In each step of the SCF procedure, a new Fock or Kohn–Sham potential is built
according to the previous density, following which the potential is diagonalized
to produce new molecular orbitals, from which a new density is computed. This
procedure is continued until either convergence is reached or a preset maximum
number of iterations is exceeded. Convergence is determined by both change in
energy and root-mean-square change in density matrix values, which must be below
the user-specified *E_CONVERGENCE* and *D_CONVERGENCE*, respectively.
The maximum number of iterations is specified by the *MAXITER* option. It
should be noted that SCF is a chaotic process, and, as such, often requires
careful selection of initial orbitals and damping during iterations to ensure
convergence. This is particularly likely for large systems, metallic systems,
multireference systems, open-shell systems, anions, and systems with diffuse
basis sets.

For initial orbital selection, several options are available. These include:

- CORE [Default]
- Diagonalization of the core Hamiltonian, removing even mean-field electron repulsion. Simple, but often too far from the final solution for larger systems. READ becomes the default for the second and later iterations of geometry optimizations.
- SAD
- Superposition of Atomic Densities. Builds the initial density as the spin-averaged sum of atomic UHF computations in the current basis. If an open-shell system, uniform scaling of the spin-averaged density matrices is performed. If orbitals are needed (e.g., in density fitting), a partial Cholesky factorization of the density matrices is used. Often extremely accurate, particularly for closed-shell systems.
- GWH
- Generalized Wolfsberg-Helmholtz, a simple Huckel-Theory-like method based on the overlap and core Hamiltonian matrices. May be useful in open-shell systems.
- READ
- Read the previous orbitals from a checkpoint file, casting from one basis to another if needed. Useful for starting anion computations from neutral orbitals, or after small geometry changes. At present, casting from a different molecular point group is not supported. This becomes the default for the second and later iterations of geometry optimizations.

These are all set by the *GUESS* keyword. Also, an automatic Python
procedure has been developed for converging the SCF in a small basis, and then
casting up to the true basis. This can be done by adding
*BASIS_GUESS* = SMALL_BASIS to the options list. We recommend the
3-21G basis for the small basis due to its efficient mix of flexibility and
compactness. An example of performing an RHF solution of water by SAD guessing
in a 3-21G basis and then casting up to cc-pVTZ is shown below:

```
molecule h2o {
0 1
O
H 1 1.0
H 1 1.0 2 104.5
}
set {
basis cc-pvtz
basis_guess 3-21G
guess sad
}
energy('scf')
```

With regard to convergence stabilization, Pulay’s Direct Inversion of the Iterative Subspace (DIIS) extrapolation, Gill’s Maximum Overlap Method (MOM), and damping are all implemented. A summary of each is presented below,

- DIIS [On by Default]
- DIIS uses previous iterates of the Fock Matrix together with an error criterion based on the orbital gradient to produce an informed estimate of the next Fock Matrix. DIIS is almost always necessary to converge the SCF procedure and is therefore turned on by default. In rare cases, the DIIS algorithm may need to be modified or turned off altogether, which may be accomplished via the options detailed below.
- MOM [Off by Default]
- MOM was developed to combat a particular class of convergence failure:
occupation flipping. In some cases, midway though the SCF procedure, a partially
converged orbital which should be occupied in the fully-optimized SCF solution
has a slightly higher orbital eigenvalue than some other orbital which should be
destined to be a virtual orbital. This results in the virtual orbital being
spuriously occupied for one or more iterations. Sometimes this resolves itself
without help, other times the occupation flips back and forth between two, four,
or more orbitals. This is typically visible in the output as a non-converging
SCF which eventually settles down to steady oscillation between two (or more)
different total energies. This behavior can be ameliorated by choosing occupied
orbitals by “shape” instead of by orbital eigenvalue, i.e., by choosing the set
of new orbitals which looks most like some previously known “good” set. The
“good” set is typically the occupied orbitals from an one of the oscillating
iterations with the lowest total energy. For an oscillating system where the
lowest total energy occurs on iterations , invoking
*MOM_START*can often rescue the convergence of the SCF. MOM can be used in concert with DIIS, though care should be taken to not turn MOM on until the oscillatory behavior begins. - Damping [Off by Default]
- In some cases, a static mixing of Fock Matrices from adjacent iterations can
quench oscillations. This mixing, known as “damping” can be activated by setting
the
*DAMPING_PERCENTAGE*keyword to a nonzero percent.

The key difficulty in the SCF procedure is treatment of the four-index ERI
contributions to the Fock Matrix. A number of algorithms are available in
PSI4 for these terms. The algorithm is selected by the *SCF_TYPE*
keyword, which may be one of the following

- PK [
*Default*] - An out-of-core, presorted algorithm using exact ERIs. Quite fast for a zero-error algorithm if enough memory is available. Integrals are generated only once, and symmetry is utilized to reduce number of integrals.
- OUT_OF_CORE
- An out-of-core, unsorted algorithm using exact ERIs. Overcomes the memory bottleneck of the current PK algorithm. Integrals are generated only once, and symmetry is utilized to reduce number of integrals.
- DIRECT
- A threaded, sieved, integral-direct algorithm, with full permutational
symmetry. This algorithm is brand new, but seems to be reasonably fast
up to 1500 basis function, uses zero disk, and can obtain significant
speedups with negligible error loss if the
*INTS_TOLERANCE*value is set to 1.0E-8 or so. - DF [
*Default*] - A density-fitted algorithm designed for computations with thousands of
basis functions. This algorithm is highly optimized, and is threaded
with a mixture of parallel BLAS and OpenMP. Note that this algorithm
should use the -JKFIT series of auxiliary bases,
*not*the -RI or -MP2FIT bases. The default guess for auxiliary basis set should work for all Dunning bases, otherwise the*DF_BASIS_SCF*keyword can be used to manually specify the auxiliary basis. This algorithm is preferred unless either absolute accuracy is required [CCSD(T)] or a -JKFIT auxiliary basis is unavailable for the primary basis/atoms involved. - CD
- A threaded algorithm using approximate ERI’s obtained by Cholesky
decomposition of the ERI tensor. The accuracy of the Cholesky
decomposition is controlled by the keyword
*CHOLESKY_TOLERANCE*. This algorithm is similar to the DF algorithm, but it is not suitable for gradient computations. The algorithm to obtain the Cholesky vectors is not designed for computations with thousands of basis functions.

For some of these algorithms, Schwarz and/or density sieving can be used to
identify negligible integral contributions in extended systems. To activate
sieving, set the *INTS_TOLERANCE* keyword to your desired cutoff
(1.0E-12 is recommended for most applications).

Recently, we have added the automatic capability to use the extremely fast DF
code for intermediate convergence of the orbitals, for *SCF_TYPE* other
than `DF`. At the moment, the code defaults to cc-pVDZ-JKFIT as the
auxiliary basis, unless the user specifies *DF_BASIS_SCF* manually. For
some atoms, cc-pVDZ-JKFIT is not defined, so this procedure will fail. In these
cases, you will see an error message of the form:

```
RuntimeError: sanity check failed! Gaussian94BasisSetParser::parser:
Unable to find the basis set for HE
```

This failure can be fixed by either setting *DF_BASIS_SCF* to an auxiliary
basis set defined for all atoms in the system, or by setting *DF_SCF_GUESS*
to false, which disables this acceleration entirely.

Ab Initio Method |
Calculation Type | E_CONVERGENCE |
D_CONVERGENCE |
SCF_TYPE |
---|---|---|---|---|

SCF of HF or DFT | energy | 6 | 6 | DF |

optimization | 8 | 8 | ||

frequency [7] | 8 | 8 | ||

SCF of post-HF | energy | 8 | 8 | PK [3] |

optimization | 10 | 10 | ||

frequency [7] | 10 | 10 | ||

CC property [2] | 10 | 10 |

Ab Initio Method |
Calculation Type | E_CONVERGENCE [5] | R_CONVERGENCE [6] |
---|---|---|---|

post-HF of post-HF | energy | 6 | |

optimization | 8 | ||

frequency [7] | 8 | ||

CC property [2] | 8 |

Footnotes

[1] | Note that this table applies only the SCF module, not to the final convergence criteria for post-HF methods or to methods that use an alternate starting point, like MCSCF. SAPT computations, too, set tighter values. |

[2] | (1, 2) This applies to properties computed through the property() function. |

[3] | Post-HF methods that do not rely upon the usual 4-index AO integrals use a density-
fitted SCF reference. That is, for DF-MP2 and SAPT, the default SCF_TYPE is DF. |

[4] | Note that this table applies to the final convergence criteria for
all the post-SCF modules that define a E_CONVERGENCE keyword. |

[5] | The E_CONVERGENCE keyword is implemented for most post-SCF modules.
See a list beginning at E_CONVERGENCE. |

[6] | The R_CONVERGENCE keyword places a convergence check on an internal
residual error measure and is implemented for several post-SCF
modules (see list beginning at R_CONVERGENCE). It is defined
according to the quantum chemical method and so its default value is set
by each module individually. |

[7] | (1, 2, 3) For frequency computations by finite difference of energies,
convergence criteria are tightened further still to 10 for
E_CONVERGENCE and D_CONVERGENCE for SCF of HF or DFT, 11
for E_CONVERGENCE and D_CONVERGENCE for SCF of post-HF,
and 10 for E_CONVERGENCE for post-HF of post-HF. |

The SCF code is already quite flexible and powerful, with new features being added weekly. We have tried as much as possible to keep the number of options to a minimum, and to allow all options to be used in the presence of all other options. Below are some rough words of advice about using the SCF code for practical calculations:

- For
*GUESS*, the`SAD`guess is usually your friend, even for open-shell systems (at the very least, it gets the right number of electrons, unlike some other programs). For instance, we have found that a simple SAD guess is often as good as doing a full SCF in a 3-21G basis and then performing a cast-up, at a fraction of the cost. However, SAD and DOCC/SOCC arrays do not play very well together at the moment. Also, the SAD UHF guess is very slow in large basis sets, so you may want to cast up for >TZ. - For wall time,
`DF`may be a factor of ten or more faster than the exact integral technologies available in PSI4. Use`DF`unless you need absolute accuracy or do not have a -JKFIT auxiliary set for your primary basis/atom type. Then use`DIRECT`. - Don’t mess with the DIIS convergence options unless convergence is a problem. We have optimized the parameters for efficiency over a wide array of system types.
- Buy a developer a beer!

The “best-practice” input file for HF is:

```
memory 1 GB # As much as you've got, the DF algorithm can use
molecule {
O
H 1 1.0
H 1 1.0 2 104.5
}
set {
basis cc-pvdz
scf_type df
guess sad
ints_tolerance 1.0E-10 # Even this is epically tight, 1.0E-8 is OK
}
energy('scf')
```