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(May 16, 2021)

Working with Prof. Head-Gordon at Berkeley, Dr. D. W. Small and Joonho Lee
have developed and implemented a novel single-reference coupled-cluster method
with singles and doubles, called CCVB-SD.
^{
1017
}
J. Chem. Phys.

(2012),
137,
pp. 114103.
Link
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634
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J. Chem. Theory Comput.

(2017),
13,
pp. 602.
Link
CCVB-SD
improves upon a more crude model CCVB (Section 6.18.2) and can be
considered a simple modification to restricted CCSD (RCCSD). CCVB-SD inherits
good properties from CCVB and RCCSD; it is spin-pure, size-extensive, and
capable of breaking multiple bonds as long as only the valence space is
correlated. It is a full doubles model and thus scales $\mathcal{O}({N}^{6})$.
However, its energy is invariant under rotations in occupied space and virtual
space, which makes it much more black-box than CCVB. Its energy function
follows

$${E}_{\mathrm{CCVB}-\mathrm{SD}}={\u27e8{\mathrm{\Phi}}_{0}\left(1+\widehat{\mathrm{\Lambda}}\right)\left|\widehat{H}\right|\left(\mathrm{exp}\left(\widehat{T}\right)-{\widehat{\text{I}}}_{\text{S}}\frac{{\widehat{Q}}^{2}}{2}\right){\mathrm{\Phi}}_{0}\u27e9}_{C}$$ | (6.53) |

where ${\widehat{\text{I}}}_{\text{S}}$ is a singlet projection operator and $\widehat{Q}$ is a quintet doubles operator. Unlike QCCD, CCVB-SD improves the right eigenfunction while leaving the left eigenfunction unchanged. The quintet term in Eq. (6.53) represents approximate connected quadruples which are responsible for describing strong correlation. The cost of CCVB-SD is only twice as expensive as RCCSD, and it is better suited for strong correlation than QCCD/VQCCD in the sense that the method becomes exact at the dissociation limits of most multiple bond breaking whereas QCCD does not except special cases.

Although CCVB-SD can be used without the active space constraints, we recommend that users use it with the valence active space in general. For benchmarking purposes, using a minimal basis will automatically provide the valence space correctly with frozen cores. Both the energy and nuclear gradients of CCVB-SD are available through CCMAN2.

It should be noted that there is no orbital optimization implemented for
CCVB-SD at the moment. This means that using basis sets larger than minimal
basis requires choosing right valence orbitals to use. Therefore, we recommend
that users run GVB-PP (or CCVB) to obtain orbitals to begin with. Orbital
optimization (*i.e.* CCVB-OD) will soon be implemented and running CCVB-OD will
be much more black-box than CCVB-SD as it does not require selecting proper
valence space orbitals.

Furthermore, CCVB-SD can be applied to only closed-shell molecules at the moment. The extension to open-shell molecules is under development.

$comment CCVB-SD job for benzene computing energy+gradients. It will also print out natural orbital occupation numbers (NOONs) $end $molecule 0 1 C 0.000000 0.698200 0.000000 C 0.000000 -0.698200 0.000000 C 1.209318 1.396400 0.000000 C 1.209318 -1.396400 0.000000 C 2.418636 0.698200 0.000000 C 2.418636 -0.698200 0.000000 H -0.931410 1.235950 0.000000 H -0.931410 -1.235950 0.000000 H 1.209318 2.471900 0.000000 H 1.209318 -2.471900 0.000000 H 3.350046 1.235950 0.000000 H 3.350046 -1.235950 0.000000 $end $rem JOBTYPE force BASIS sto-3g METHOD ccvbsd THRESH 14 SCF_ALGORITHM gdm SCF_CONVERGENCE 10 CC_REF_PROP true SYMMETRY false SYM_IGNORE true $end