Search Results


7.11 Coupled-Cluster Excited-State and Open-Shell Methods


(April 13, 2024)

Double-ionization potential (DIP) is another non-electron-conserving variant of EOM-CCSD. 669 Kuś T., Krylov A. I.
J. Chem. Phys.
(2011), 135, pp. 084109.
, 670 Kuś T., Krylov A. I.
J. Chem. Phys.
(2012), 136, pp. 244109.
In DIP, target states are reached by detaching two electrons from the reference state:

Ψk=R^N-2Ψ0(N+2), (7.57)

and the excitation operator R has the following form:

R^=12ijrijji+16ijkarijkaakji. (7.58)

As a reference state in the EOM-DIP calculations one usually takes a well-behaved closed-shell state. EOM-DIP is a useful tool for describing molecules with electronic degeneracies of the type “2n-2 electrons on n degenerate orbitals”. The simplest examples of such systems are diradicals with two-electrons-on-two-orbitals pattern. Moreover, DIP is a preferred method for four-electrons-on-three-orbitals wave functions.

Accuracy of the EOM-DIP-CCSD method is similar to accuracy of other EOM-CCSD models, i.e., 0.1–0.3 eV. The scaling of EOM-DIP-CCSD is 𝒪(N6), analogous to that of other EOM-CCSD methods. However, its computational cost is less compared to, e.g., EOM-EE-CCSD, and it increases more slowly with the basis set size. An EOM-DIP calculation is invoked by using DIP_STATES, or DIP_SINGLETS and DIP_TRIPLETS. In certain circumstances, the DIP_AA_STATES, DIP_BB_STATES, DIP_BA_STATES keywords can be used.

Note:  The performance of EOM-DIP may be poor if the reference state is unstable with respect to electron detachment. See Section 7.11.12 for details.

Note:  In some applications of EOM-DIP-CCSD, only 2h operators were included in the EOM part. These calculations correspond to energies obtained from EOM_PRECONV_DOUBLES = TRUE calculation.