Communication: The pole structure of the dynamical polarizability tensor in equation-of-motion coupled-cluster theory

摘要

In this letter, we investigate the pole structure of dynamical polarizabilities computed within the equation-of-motion coupled-cluster (EOM-CC) theory. We show, both theoretically and numerically, that approximate EOM-CC schemes such as, for example, the EOM-CC singles and doubles model exhibit an incorrect pole structure in which the poles that reflect the excitations from the target state (i.e., the EOM-CC state) are supplemented by artificial poles due to excitations from the CC reference state. These artificial poles can be avoided by skipping the amplitude response and reverting to a sum-over-states formulation. While numerical results are generally in favor of such a solution, its major drawback is that this scheme violates size extensivity. Published by AIP Publishing.