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1.
J Chem Phys ; 159(13)2023 Oct 07.
Artículo en Inglés | MEDLINE | ID: mdl-37787129

RESUMEN

The Unitary Group Adaptation (UGA) offers a very compact and efficient spin adaptation strategy for any spin-free Hamiltonian in a many body framework. Our use of UGA in the context of state-specific (SS) Jeziorski-Monkhorst Ansatz based multireference coupled cluster (MRCC) theory obviates the non-commutativity between the spin-free cluster operators via a normal ordered exponential parametrization in the wave operator. A previous formulation of UGA-SSMRCC by us [R. Maitra, D. Sinha, and D. Mukherjee, J. Chem. Phys. 137, 024105 (2012)], using the same ansatz, employed certain sufficiency conditions to reach the final working equations, which cannot be improved systematically. In this article, we will present a more rigorous formulation that follows from an exact factorization of the unlinked terms of the Bloch equation, resulting in equations on which a hierarchy of approximations can be systematically performed on the emergent additional terms. This derivation was shown in our recent article [D. Chakravarti, S. Sen, and D. Mukherjee, Mol. Phys. 119, e1979676 (2021)] in the context of a single open shell CC formalism and was applied to spectroscopic energy differences where the contribution of the new terms was found to be of the order of ∼0.001 eV for ionization potential, electron affinity, and excitation energy. In the current work, we will present a comparison between the earlier and current formulations via both a theoretical analysis and a numerical demonstration of the dramatic effect of the additional terms brought in by the factorization on potential energy curves. The contribution of such terms was found to gain importance with an increase in the number of singly occupied active orbitals in the model space functions.

2.
J Chem Phys ; 155(1): 014101, 2021 Jul 07.
Artículo en Inglés | MEDLINE | ID: mdl-34241385

RESUMEN

The Unitary Group Adapted State-Specific Multi-Reference Perturbation Theory (UGA-SSMRPT2) developed by Mukherjee et al. [J. Comput. Chem. 36, 670 (2015)] has successfully realized the goal of studying bond dissociation in a numerically stable, spin-preserving, and size-consistent manner. We explore and analyze here the efficacy of the UGA-SSMRPT2 theory in the description of the avoided crossings and interlacings between a manifold of potential energy curves for states belonging to the same space-spin symmetry. Three different aspects of UGA-SSMRPT2 have been studied: (a) We introduce and develop the most rigorous version of UGA-SSMRPT2 that emerges from the rigorous version of UGA-SSMRCC utilizing a linearly independent virtual manifold; we call this the "projection" version of UGA-SSMRPT2 (UGA-SSMRPT2 scheme P). We compare and contrast this approach with our earlier formulation that used extra sufficiency conditions via amplitude equations (UGA-SSMRPT2 scheme A). (b) We present the results for a variety of electronic states of a set of molecules, which display the striking accuracy of both the two versions of UGA-SSMRPT2 with respect to three different situations involving weakly avoided crossings, moderate/strongly avoided crossings, and interlacing in a manifold of potential energy curves (PECs) of the same symmetry. Accuracy of our results has been benchmarked against IC-MRCISD + Q.

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