Abstract
A brief description of basic models and methods that are currently exploited in molecular electronic structure calculations indicates the desirability of extending the single-reference coupled-cluster (CC) approach to the multi-reference (MR) case. The recently developed explicit formalism of orthogonally spin-adapted, state-universal (or Hilbert space) MR-CC theory for the special case of closed-shell type references is applied to a simple four-electron model system formed by two interacting hydrogen molecules. Varying the geometry of the nuclear framework from the square configuration to a linear one this model simulates the breaking of a single chemical bond and enables a continuous transition to be made between the degenerate and non-degenerate regimes. The simplicity of the model enables a comparison with the exact solution, obtained by the full configuration interaction method. In this way the performance of the MR-CC approach at both linear and non-linear levels of approximation, nature and multiplicity of MR-CC solutions and the role played by the intruder states can be examined in considerable detail.
Keywords
- Configuration Interaction
- Bilinear Term
- Full Configuration Interaction
- Internuclear Separation
- Intruder State
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Paldus, J., Piecuch, P., Jeziorski, B., Pylypow, L. (1992). Extension of Coupled Cluster Methodology to Open Shells: State Universal Approach. In: Ainsworth, T.L., Campbell, C.E., Clements, B.E., Krotscheck, E. (eds) Recent Progress in Many-Body Theories. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3466-2_19
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