Chapter 4
Equation-of-Motion Coupled-Cluster Models
Monika Musiał,
Monika Musiał
Institute of Chemistry, University of Silesia in Katowice, Szkolna 9, 40-006 Katowice, Poland
Search for more papers by this authorMonika Musiał,
Monika Musiał
Institute of Chemistry, University of Silesia in Katowice, Szkolna 9, 40-006 Katowice, Poland
Search for more papers by this authorBook Editor(s):Leticia González,
Roland Lindh,
Leticia González
Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Austria
Search for more papers by this authorRoland Lindh
Department of Chemistry – BMC, Uppsala University, Sweden
Search for more papers by this authorSummary
Various computational schemes hidden under the name EOM-CC (equation-of-motion coupled-cluster) create a path through which the CC theory is applied to investigate excited, ionized and electron-attached molecular systems. In this chapter we consider five realizations of the EOM-CC approach focused on the studies of electronic excitations (EE), ionization potentials (IP), electron-attached (EA) states, double ionization potentials (DIP) and double-electron-attached (DEA) states. The direct application of the considered methods allows to study electronic states of the reference system as well as those differing from the reference by one (IP, EA) or two (DIP, DEA) electrons. In addition we propose an indirect application of the EOM-CC schemes which in some cases may be more interesting than the direct one. Namely, when the open-shell system A is studied then we may adopt as the reference one of its charged analogues: A+, A−, A2+, A2−on condition that it represents the closed-shell structure implying using the restricted Hartree-Fock (HF) reference. Then to recover the data relevant to the neutral system A we need to apply the EA, IP, DEA or DIP variant of the EOM-CC scheme, respectively. This can be generalized in the following way: to study with the EOM-CC approach the system A (charged or neutral) we may select as the reference that form of A which is of closed-shell character and differs from A by no more than 2 electrons. Then by using one of the EOM variants listed above we may recover an original structure. Owing to that we may avoid calculations based on the potentially spin-contaminated unrestricted HF reference. Moreover, the DIP and DEA approaches open the way to describe in a correct way a homolytic dissociation of the single bond without necessity to deal with the open-shell products. For all five considered methods (i.e., EE-EOM-CC, IP-EOM-CC, DIP-EOM-CC, EA-EOM-CC, DEA-EOM-CC) we provide detailed working equations both at the CCSD and CCSDT level in the form ready to code. For each of the considered EOM schemes we give illustrative results which make it possible to compare the performance of the E0M-CCSD and EOM-CCSDT approaches.
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