Abstract
We present a method that accurately describes strongly correlated states and captures dynamical correlation. It is derived as a modification of coupled-cluster theory with single and double excitations (CCSD) through consideration of particle distinguishability between dissociated fragments, whilst retaining the key desirable properties of particle-hole symmetry, size extensivity, invariance to rotations within the occupied and virtual spaces, and exactness for two-electron subsystems. The resulting method, called the distinguishable cluster approximation, smoothly dissociates difficult cases such as the nitrogen molecule, with the modest N-6 computational cost of CCSD. Even for molecules near their equilibrium geometries, the new model outperforms CCSD. It also accurately describes the massively correlated states encountered when dissociating hydrogen lattices, a proxy for the metal-insulator transition, and the fully dissociated system is treated exactly. (C) 2013 AIP Publishing LLC.
Original language | English |
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Article number | 021102 |
Number of pages | 4 |
Journal | Journal of Chemical Physics |
Volume | 139 |
Issue number | 2 |
DOIs | |
Publication status | Published - 14 Jul 2013 |
Keywords
- MATRIX RENORMALIZATION-GROUP
- COUPLED-CLUSTER
- IDENTICAL PARTICLES
- QUANTUM-CHEMISTRY
- FORMULATION