Published August 27, 2013
| Version v1
Journal article
Open
Communication: Analytic gradients in the random-phase approximation
Authors/Creators
- 1. University of Oslo 1 Centre for Theoretical and Computational Chemistry, Department of Chemistry, , P.O. Box 1033 Blindern, N-0315 Oslo, Norway
- 2. Università degli Studi di Trieste 2 Dipartimento di Scienze Chimiche e Farmaceutiche, , Via Licio Giorgieri 1, IT-34127 Trieste, Italy
- 3. University Park 3 School of Chemistry, University of Nottingham, , Nottingham NG7 2RD, United Kingdom
Description
The relationship between the random-phase-approximation (RPA) correlation energy and the continuous algebraic Riccati equation is examined and the importance of a stabilizing solution is emphasized. The criterion to distinguish this from non-stabilizing solutions can be used to ensure that physical, smooth potential energy surfaces are obtained. An implementation of analytic RPA molecular gradients is presented using the Lagrangian technique. Illustrative calculations indicate that RPA with Hartree-Fock reference orbitals delivers an accuracy similar to that of second-order Møller–Plesset perturbation theory.
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