7.7 Correlated Excited State Methods: The CIS(D) Family

7.7.4 SOS-CIS(D0) Model

CIS(D) and its cousins explained in the above are all based on a second-order non-degenerate perturbative correction scheme on the CIS energy (“diagonalize-and-then-perturb” scheme). Therefore, they may fail when multiple excited states come close in terms of their energies. In this case, the system can be handled by applying quasi-degenerate perturbative correction scheme (“perturb-and-then-diagonalize” scheme). The working expression can be obtained by slightly modifying CIS(D) expression shown in Section 7.7.1.353

First, starting from Eq. (7.35), one can be explicitly write the CIS(D) energy as144, 353

ωCIS+ω(2)=𝐛(𝟎)𝐭𝐀SS(0)𝐛(𝟎)+𝐛(𝟎)𝐭𝐀SS(2)𝐛(𝟎)-𝐛(𝟎)𝐭𝐀SD(1)(𝐃DD(0)-ωCIS)-1𝐀DS(1)𝐛(𝟎) (7.41)

To avoid the failures of the perturbation theory near degeneracies, the entire single and double blocks of the response matrix should be diagonalized. Because such a diagonalization is a non-trivial non-linear problem, an additional approximation from the binomial expansion of the (𝐃DD(0)-ωCIS)-1 is further applied:353

(𝐃DD(0)-ωCIS)-1=(𝐃DD(0))-1(1+ω(𝐃DD(0))-1+ω2(𝐃DD(0))-2+) (7.42)

The CIS(D0) energy ω is defined as the eigen-solution of the response matrix with the zero-th order expansion of this equation. Namely,

(𝐀SS(0)+𝐀SS(2)-𝐀SD(1)(𝐃DD(0))-1𝐀DS(1))𝐛=ω𝐛 (7.43)

Similar to SOS-CIS(D), SOS-CIS(D0) theory is defined by taking the opposite-spin portions of this equation and then scaling them with two semi-empirical parameters:144

(𝐀SS(0)+cT𝐀SSOS(2)-cU𝐀SDOS(1)(𝐃DD(0))-1𝐀DSOS(1))𝐛=ω𝐛 (7.44)

Using the Laplace transform and the auxiliary basis expansion techniques, this can also be handled with a 4th-order scaling computational effort. In Q-Chem, an efficient 4th-order scaling analytical gradient of SOS-CIS(D0) is also available. This can be used to perform excited state geometry optimizations on the electronically excited state surfaces.