Inactive excitations in Mukherjee's state-specific multireference coupled cluster theory treated with internal contraction: development and applications.

Abstract

One generic difficulty of most state-specific many-body formalisms using the Jeziorski-Monkhorst ansatz: ψ = Σ(μ)exp(T(μ))|φ(μ)>c(μ) for the wave-operators is the large number of redundant cluster amplitudes. The number of cluster amplitudes up to a given rank is many more in number compared to the dimension of the Hilbert Space spanned by the virtual functions of up to the same rank of excitations. At the same time, all inactive excitations--though linearly independent--are far too numerous. It is well known from the success of the contracted multi-reference configuration interaction (MRCI(SD)) that, at least for the inactive double excitations, their model space dependence (μ-dependence) is weak. Considerable simplifications can thus be obtained by using a partially internally contracted description, which uses the physically appealing approximation of taking the inactive excitations T(i) to be independent of the model space labels (μ-independent). We propose and implement in this paper such a formalism with internal contractions for inactive excitations (ICI) within Mukherjee's state-specific multi-reference coupled cluster theory (SS-MRCC) framework (referred to from now on as the ICI-SS-MRCC). To the extent the μ-independence of T(i) is valid, we expect the ICI-SS-MRCC to retain the conceptual advantages of size-extensivity yet using a drastically reduced number of cluster amplitudes without sacrificing accuracy. Moreover, greater coupling is achieved between the virtual functions reached by inactive excitations as a result of the internal contraction while retaining the original coupling term for the μ-dependent excitations akin to the parent theory. Another major advantage of the ICI-SS-MRCC, unlike the other analogous internally contracted theories, such as IC-MRCISD, CASPT2, or MRMP2, is that it can use relaxed coefficients for the model functions. However, at the same time it employs projection manifolds for the virtuals obtained from inactive n hole-n particle (nh-np) excitations on the entire reference function containing relaxed model space coefficients. The performance of the method has been assessed by applying it to compute the potential energy surfaces of the prototypical H(4); to the torsional potential energy barrier for the cis-trans isomerism in C(2)H(4) as well as that of N(2)H(2), automerization of cyclobutadiene, single point energy calculation of CH(2), SiH(2), and comparing them against the SS-MRCC results, benchmark full CI results, wherever available and those from the allied MR formalisms. Our findings are very much reminiscent of the experience gained from the IC-MRCISD method.