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Although it is quite promising to compute the spectroscopic energies [say, ionization potential (IP)] via the traditional valence-universal multireference coupled cluster (VUMRCC) method based on the description of the complete model space being seriously plagued by the perennial intruder state problem, the eigenvalue independent partitioning (EIP) based VUMRCC (coined as EIP-MRCC) method is quite effective to predict the spectroscopic energies in an intruder-free manner. Hence, the EIP-MRCC method is suitable for generating both the principal IPs and the satellite IPs of the inner-valence region. An EIP strategy converts the nonlinear VUMRCC equations for M(m,n) dimensional model space of m hole and n particle to a non-Hermitian eigenproblem of larger dimension whose M(m,n) roots are only physically meaningful. To increase the quality of the computed energy differences in the sense of chemical accuracy and to locate the correct position of it in the spectrum, the inclusion of higher-body cluster operators on top of all the standard singles-doubles is not the only pivotal issue, the effect of the size of the basis set is also equally important. This paper illustrates these issues by calculating the principal and satellite IPs of HF and HCl molecules using various basis sets (viz., Dunning's cc-pVDZ, cc-pVTZ, and cc-pVQZ) via EIP-MRCC method with full inclusion of triples (abbreviated as EIP-MRCCSDT). The results seem quite encouraging in comparison with the experimental values. The controversial 2Π satellite at 28.67 eV of HCl of Svensson et al. [J. Chem. Phys. 89, 7193 (1988)] is also reported. [ABSTRACT FROM AUTHOR]

A multireference coupled-cluster (MRCC) formulation for the direct calculation of excitation energies and ionization potentials is presented. The reference space connects a set of p–h excited determinants built from all the set of active particles and holes in the model space. This model space is incomplete, requiring a Fock-space approach and the postulate of a ‘‘universal’’ wave operator to arrive at a linked diagram expression for the effective Hamiltonian Heff, whose eigenvalues are the excitation energies for the problem. Use of a normal-ordered exponential cluster ansatz allows one to construct, hierarchically, the CC equations for the p–h model space starting from the ground state. We present an extension of an earlier formulation for excitation energies that allows us to have both active and inactive particles and holes in our method. Numerical applications are reported for the prototypical small molecules CO and N2. [ABSTRACT FROM AUTHOR]

A valence-universal multireference coupled cluster (VUMRCC) theory, realized via the eigenvalue independent partitioning (EIP) route, has been implemented with full inclusion of triples excitations for computing and analyzing the entire main and several satellite peaks in the ionization potential spectra of several molecules. The EIP-VUMRCC method, unlike the traditional VUMRCC theory, allows divergence-free homing-in to satellite roots which would otherwise have been plagued by intruders, and is thus numerically more robust to obtain more efficient and dependable computational schemes allowing more extensive use of the approach. The computed ionization potentials (IPs) as a result of truncation of the (N-1) electron basis manifold involving virtual functions such as 2h-p and 3h-2p by different energy thresholds varying from 5 to 15 a.u. with 1 a.u. intervals as well as thresholds such as 20, 25, and 30 a.u. have been carefully looked into. Cutoff at around 25 a.u. turns out to be an optimal threshold. Molecules such as C2H4 and C2H2 (X = D,T), and N2 and CO (X = D,T,Q) with Dunning's cc-pVXZ bases have been investigated to determine all main and 2h-p shake-up and 3h-2p double shake-up satellite IPs. We believe that the present work will pave the way to a wider application of the method by providing main and satellite IPs for some problematic N-electron closed shell systems., (Copyright © 2013 Wiley Periodicals, Inc.)