Amplitude Determinant Coupled Cluster with Pairwise Doubles

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• 作者：Luning Zhao ; Eric Neuscamman
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2016
• 出版时间：December 13, 2016
• 年：2016
• 卷：12
• 期：12
• 页码：5841-5850
• 全文大小：527K
• ISSN：1549-9626

文摘

Recently developed pair coupled cluster doubles (pCCD) theory successfully reproduces doubly occupied configuration interaction (DOCI) with mean field cost. However, the projective nature of pCCD makes the method nonvariational and thus hard to improve systematically. As a variational alternative, we explore the idea of coupled-cluster-like expansions based on amplitude determinants and develop a specific theory similar to pCCD based on determinants of pairwise doubles. The new ansatz admits a variational treatment through Monte Carlo methods while remaining size-consistent and, crucially, polynomial cost. In the dissociations of LiH, HF, H₂O, and N₂, the method performs very similarly to pCCD and DOCI, suggesting that coupled-cluster-like ansatzes and variational evaluation may not be mutually exclusive. In an attractive pairing model, the method retains its accuracy even when pCCD suffers a severe variational violation.