Similarity-transformed equation of motion

M. Nooijen and R. J. Bartlett,/. Chem. Phys., 107, 6812 (1997). Similarity-Transformed Equation-of-Motion Coupled-Cluster Theory Details, Examples, And Comparisons. 

Nooijen M, Bartlett RJ (1997) Similarity transformed equation-of-motion coupled-cluster theory Details, examples, and comparisons. J Chem Phys 107 6812-6830. 

A similarity-transformed equation-of-motion coupled-cluster (STEOM-CC) study of excited states <1997JCP6812> has been applied to calculate the vertical excitation spectra and various 0-0 transitions of selected... 

Fig. 1 for planar and axisymmetric (cylindrical) propagation. These were obtained by analytic (planar case) or numerical (cylindrical case) solution of the similarity-transformed equations of motion. The similarity variable f = xjUcjt. The fluid returns to rest and forms an expanding zone of motionless fluid that extends over about one-half of the distance to which the detonation has progressed at any given time. The fluid state immediately behind the detonation wave is approxi-... 

Sous J, Goel P, Nooijen M. Similarity transformed equation of motion coupled cluster theory revisited a benchmark study of valence excited states. Mol Phys. 2013 112 616-638. Trofimov AB, Krivdina IL, Weller J, Schimer J. Algebraic-diagrammatic construction propagator approach to molecular response properties. Chem Phys. 2006 329 1-10. 

Another category of approaches that avoids the symmetry breaking problem of the orbitals for the target state is based on using a related, well-behaved HF reference instead. Examples of such techniques include quasi-restricted Hartree-Fock coupled-cluster (QRHF CC) (11,19), symmetry adapted cluster configuration interaction (SAC-CI) (22,23), coupled-cluster linear response theory (CCLRT) (24-26) or equivalently equation-of-motion coupled-cluster (EOM-CC) (27-32), Fock space multi-reference coupled-cluster (FSMRCC) (33-37), and similarity transformed equation-of-motion coupled-cluster (STEOM-CC) (38-40). In the case of NO3 and N03, the restricted Hartree-Fock (RHF) orbitals of the closed-shell N03 anion system can be used as the reference. The anion orbitals are stable with respect to symmetry perturbations, and the system does not suffer from the artifactual symmetry breaking of the neutral and cation. 

The symmetry-correct anion orbitals can also be utilized in calculations of states of the N03 cation. The primary purpose of this work is to examine the NO3 ionization spectrum and the ground and low excited states of the N03 cation system by the DIP-STEOM-CCSD method (40) (double ionization potential similarity transformed equation-of-motion coupled-cluster singles and doubles). The DIP-STEOM-CCSD method is built upon the IP-EOM-CCSD method (32) (ionization potential equation-of-motion coupled-cluster singles and doubles), which in turn, has been shown to be equivalent (41,42) to singly ionized FSMRCC, such as the example of Kaldor above. The DIP-STEOM-CCSD method generates ground and excited states of the cation by deletion of... 

Of the 33 invited speakers and the seven who contributed talks, 17 accepted our invitation to contribute a chapter to this book. These chapters are complemented by three additional chapters from individuals to help develop a more cohesive book as well as an overview chapter. Approximately half of the chapters are focused on the development of ab initio electronic structure methods and consideration of specific challenging molecular systems using electronic structure theory. Some of these chapters document the dramatic developments in the range of applicability of the coupled-cluster method, including enhancements to coupled-cluster wavefunctions based on additional small multireference configuration interaction (MR-CISD) calculations, the method of moments, the similarity transformed equation of motion (STEOM) method, a state-specific multireference coupled-cluster method, and a computationally efficient approximation to variational coupled-cluster theory. The concentration on the coupled-cluster approach is balanced by an approximately equal number of chapters discussing other aspects of modem electronic stracture theory. In particular, other methods appropriate for the description of excited electronic states, such as multireference... 

We have found the principal axes from the equation of motion in an arbitrary coordinate system by means of a similarity transformation S KS (Chapter 2) on the coefficient matrix for the quadratic containing the mixed terms... 

Although diagrams like Fig. 6.1 are especially convenient to illustrate the qualitative features of TST and VTST, the solution of the equations of motion in (rAB,rBc) coordinates is complicated due to cross terms coupling the motions of the different species. It is for that reason we introduced mass scaled Jacobi coordinates in order to simplify the equations of motion. So, one now asks what does the potential function for reaction between A and BC look like in these new mass scaled Jacobi coordinates. To illustrate we construct a graph with axes designated rAB and rBc within the (x,y) coordinate system. In the x,y space lines of constant y are parallel to the x axis while lines of constant x are parallel to the y axis. The rAB and rBc axes are constructed in similar fashion. Lines of constant rBc are parallel to the rAB axis while lines of constant rAB are parallel are parallel to the rBc axis. From the above transformation, Equations 6.10 to 6.13... 

Stanton JF, Gauss J (1995) Perturbative treatment of the similarity transformed Hamiltonian in equation-of-motion coupled-cluster approximations. J Chem Phys 103 1064-1076. 

It can now be shown that the Hamiltonian equations are equivalent to the more familiar Newton s second law of motion in Newtonian mechanics, adopting a transformation procedure similar to the one used assessing the Lagrangian equations. In this case we set pi = ri and substitute both the Hamiltonian function H (2.22) and subsequently the Lagrangian function L (2.6) into Hamilton s equations of motion. The preliminary results can be expressed as... 

Similarly, it can be shown that Eq. [55] is a statement of the preservation of phase space volume under propagation by Hamilton s equations of motion, that is, Liouville s theorem. It is important to note that the Poincare integral invariants are also preserved under a canonical transformation of any kind and not just the propagation of Hamilton s equations. 

A third procedure for calculating correlated frequency-dependent properties is the coupled-cluster, equations-of-motion (CC-EOM) method. This approach is formally equivalent to solving the sum-over-states expression using a similarity transformed Hamiltonian, H = e He, where the transformation is obtained from the coupled cluster choice for a reference state,... 

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