7 Open-Shell and Excited-State Methods

7.7 Square Gradient Minimization for Calculation of ΔSCF and ROKS Excited States

Standard TDDFT is prone to catrastrophic failure in regimes where there is a substantial difference in density between ground and excited states, such as charge-transfer, Rydberg, or core excitations.Dreuw:2005 This can be greatly ameliorated via inclusion of orbital relaxation beyond linear response, via explict optimization of excited state orbitals in a manner analogous to ground state SCF. However, this is a challenging task as excited states are typically not minimums of the energy in orbital space, but are usually saddle points. Traditional orbital optimizers like DIIS or GDM therefore tend to fail in converging to excited state orbitals, and instead collapse to lower energy configurations (usually the ground state). This variational collapse problem consequently restricts the utility of excited state orbital optimized methods. The MOM approach (see Sec 7.5) can prevent this in many cases, but is constrained by the convergence issues stemming from the underlying DIIS method.

Diptarka Hait and Martin Head-Gordon presented an alternative approach to excited state orbital optimization in Ref. Hait:2020b, which avoids the challenges of energy extremization by minimizing the square of the energy gradient instead. Ground state HF and DFT approaches seek to minimize the energy E against orbital degrees of freedom θ and therefore the gradient of E against θ (θE) must be zero at convergence. It is therefore possible to obtain the same result by minimizing Δ=|θE|2 to zero. However, all stationary points of E are minimums of Δ, not just the ground state. It is therefore possible to optimize excited state orbitals by starting from a reasonable guess (such as a non-aufbau configuration corresponding to the excitation) and minimizing Δ. This avoids all the pitfalls of attempting to optimize unstable stationary points in E and thus averts variational collapse. Further details about this Square Gradient Minimization method are provided in Ref. Hait:2020b.

SGM in Q-Chem can be used to optimize orbitals for two different excited state approaches: ΔSCF and ROKS. ΔSCF simply attempts to minimize the energy of a single Slater determinant, which is often sufficient for many challenging excitations (including many double excitations as shown in Refs. Barca:2018 and Hait:2020b). However, many excitations (including all single excitations from a closed shell ground state) break electron pairs: leading to states that cannot be described with a single determinant. It is possible to spin-purify the energy of a spin-contaminated non-aufbau filled determinant post SCF, but this requires at least two separate orbital optimizations. ROKS (described in detail in Sec 7.6) offers an alternative solution to this problem by directly optimizing a single set of orbitals for which the spin-purified energy is stationary. Analytic nuclear gradients are available for both ΔSCF and ROKS, permitting geometry optimizations and ab initio molecular dynamics. Analytic frequencies are available for ΔSCF (except with functionals contain VV10 nonlocal correlation), while finite-difference frequency calculations (with IDERIV =1) could be run for ROKS (or ΔSCF with non VV10 functionals).

There are some slight differences between use of SGM for different orbital classes due to ease of implementation. ΔSCF with restricted closed-shell (R) and unrestricted (U) orbitals can be run with SCF_ALGORITHM = SGM_LS or SCF_ALGORITHM = SGM_QLS, with initial orbital occupation specified by the $occupied block (as described in Section 7.5 and the examples 7.7 and 7.7 below). ΔSCF with restricted open-shell (RO) orbitals or ROKS calculations can be performed via SCF_ALGORITHM = SGM or SCF_ALGORITHM = SGM_LS, and a reordering of orbitals to ensure that the unpaired ones lie at the frontier (as described in examples 7.7 and 7.7 below). The Δ gradient (vs θ) employed by SGM is computed analytically (except for VV10 containing functionals) for R-,U- and RO- ΔSCF, at a cost equal to a single Fock build. However, the ROKS Δ gradient (as well as the ΔSCF cases with VV10 containing functionals) is found via a finite difference approach (see Eq.4.43), which leads to the cost being equal to that of two Fock builds. Cumulatively, a single SGM iteration costs twice as much as a single GDM iteration when analytic Δ gradients are available, and three times as much if the finite difference approximation has to be used. This does not affect the overall asymptotic scaling of the calculation, however. It is worth noting that excited state convergence could take more iterations than corresponding ground state jobs, and so MAX_SCF_CYCLES should be set to a large value (like 200) instead of the default 50. SCF_CONVERGENCE = 4 (instead of the default value of 5) is also permissible if only energies are desired, as long as it is explicitly confirmed that the variation in energy over several iterations is much less than the desired accuracy after job completion (variation greater than 0.001 hartrees or 0.03 eV would be quite problematic). Lowering SCF_CONVERGENCE further however would likely significantly compromise properties like dipole moments or nuclear gradients, and is therefore not reccomended.

SCF_ALGORITHM
       Algorithm used for converging the SCF.
TYPE:
       STRING
DEFAULT:
       None
OPTIONS:
       SGM SGM_LS SGM_QLS
RECOMMENDATION:
       SGM should be used for RO-ΔSCF or ROKS calculations only. SGM_LS is reccomended for R- or U- ΔSCF, though it can also be used for RO-ΔSCF or ROKS. SGM_QLS is a slower, but more robust option for R- and U- ΔSCF calculations.

DELTA_GRADIENT_SCALE
       Scales the gradient of Δ by N/100, which can be useful for cases with troublesome convergence by reducing step size.
TYPE:
       INTEGER
DEFAULT:
       100
OPTIONS:
       N
RECOMMENDATION:
       Use default. For problematic cases 50, 25, 10 or even 1 could be useful.

ROKS
       Controls whether ROKS calculation will be performed.
TYPE:
       LOGICAL
DEFAULT:
       FALSE
OPTIONS:
       FALSE ROKS is not performed. TRUE ROKS will be performed.
RECOMMENDATION:
       Set to TRUE if ROKS calculation is desired. UNRESTRICTED = FALSE should also be ensured.

Example 7.22  Restricted ΔSCF double excitation from 2s to 2p of Be atom, using SGM_QLS and the ground state orbitals as an initial guess.

$comment
Calculates Delta-SCF excitation energy for the 2s^2 -> 2p^2 excitation of Be
using SCAN and SGM_QLS scf converger
$end

$molecule
0 1
Be
$end

$rem
method scan
basis aug-cc-pVTZ
thresh 14
scf_convergence 8
scf_algorithm diis
symmetry false
sym_ignore true
xc_grid 000099000590
gen_scfman true
$end

@@@@@@@@@

$molecule
read
$end

$rem
method scan
basis aug-cc-pVTZ
thresh 14
scf_algorithm sgm_qls
symmetry false
sym_ignore true
scf_guess read
xc_grid 000099000590
gen_scfman true
$end

$occupied
1 3
1 3
$end

Example 7.23  ROKS single excitation from HOMO to LUMO for an NH3—F2 model complex, which describes electron transfer from NH3 to F2. Ground state orbitals are used as an initial guess.

$molecule
0 1
N  0.0000   0.0000    0.0000
H  0.0000  -0.9377   -0.3816
H  0.8121   0.4689   -0.3816
H -0.8121   0.4689   -0.3816
F  0.0000   0.0000    6.0000
F  0.0000   0.0000    7.4120
$end


$rem
method pbe0
basis  cc-pVDZ
symmetry false
sym_ignore true
scf_convergence 8
$end

@@@@@@@@@@@

$comment
The reorder section is superfluous here since the excitation is HOMO to LUMO
and thus the unpaired electron orbitals are already at the frontier.
$end

$molecule
read
$end

$rem
method pbe0
basis  cc-pVDZ
symmetry false
sym_ignore true
scf_algorithm sgm
roks true
scf_guess read
$end

$reorder_mo
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
$end

Example 7.24  Unrestricted ΔSCF single excitation from HOMO-1 to LUMO+1 for HCHO using SGM_LS scf converger and the ground state orbitals as an initial guess.

$comment
Calculates Delta-SCF excitation energy for the
HOMO-1 -> LUMO+1 excitation of HCHO
 using SCAN and SGM_LS scf converger
$end

$molecule
0 1
O1      0.0000  0.0000  1.2050
C2      0.0000  0.0000  0.0000
H3      0.0000  0.9429  -0.5876
H4      0.0000  -0.9429 -0.5876
$end

$rem
method scan
basis aug-cc-pVTZ
thresh 14
scf_convergence 8
scf_algorithm diis
symmetry false
sym_ignore true
xc_grid 000099000590
gen_scfman true
$end

@@@@@@@@@

$molecule
read
$end

$rem
method scan
basis aug-cc-pVTZ
thresh 14
scf_algorithm sgm_ls
symmetry false
sym_ignore true
scf_guess read
xc_grid 000099000590
gen_scfman true
unrestricted true
scf_convergence 7
max_scf_cycles 500
$end

$occupied
1 2 3 4 5 6 8 10
1 2 3 4 5 6 7 8
$end

Example 7.25  Combined RO-ΔSCF core-ionization and 1s->LUMO+1 ROKS core excited state for HF, using SGM.

$molecule
0 1
F       0.0000  0.0000  0.0000
H       0.0000  0.0000  0.9168
$end

$rem
method scan
basis aug-cc-pCVTZ
symmetry false
$end

@@@@@@@@@@@@
$comment
Calculates the RO-DeltaSCF core ionized state. The reorder section pushes the F1s orbital
(first orbital by energy) to the frontier, instead of the HOMO (5th orbital).
$end

$molecule
1 2
F       0.0000  0.0000  0.0000
H       0.0000  0.0000  0.9168
$end

$rem
method scan
basis aug-cc-pCVTZ
unrestricted false
scf_guess read
symmetry false
scf_algorithm sgm
$end

$reorder_mo
2 3 4 5 1
2 3 4 5 1
$end
@@@@@@@@@@@@

$comment
Calculates the ROKS core excited state. The O1s orbital is in the place of the HOMO
from the previous reordering. The present reorder section pushes the LUMO+1 orbital
(the 7th orbital) to the frontier, instead of the LUMO (6th orbital).
$end

$molecule
0 1
F       0.0000  0.0000  0.0000
H       0.0000  0.0000  0.9168
$end

$rem
method scan
roks true
basis  aug-cc-pCVTZ
scf_guess read
symmetry false
scf_algorithm sgm
max_scf_cycles 200
$end

$reorder_mo
1 2 3 4 5 7 6
1 2 3 4 5 7 6
$end