論文

査読有り
2017年10月

Multistate Complete-Active-Space Second-Order Perturbation Theory Based on Density Matrix Renormalization Group Reference States

JOURNAL OF CHEMICAL THEORY AND COMPUTATION
  • Takeshi Yanai
  • ,
  • Masaaki Saitow
  • ,
  • Xiao-Gen Xiong
  • ,
  • Jakub Chalupsky
  • ,
  • Yuki Kurashige
  • ,
  • Sheng Guo
  • ,
  • Sandeep Sharma

13
10
開始ページ
4829
終了ページ
4840
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.jctc.7b00735
出版者・発行元
AMER CHEMICAL SOC

We present the development of the multistate multireference second-order perturbation theory (CASPT2) with multiroot references, which are described using the density matrix renormalization group (DMRG) method to handle a large active space. The multistate first-order wave functions are expanded into the internally contracted (IC) basis of the single-state single-reference (SS-SR) scheme, which is shown to be the most feasible variant to use DMRG references. The feasibility of the SS-SR scheme comes from two factors: first, it formally does not require the fourth-order transition reduced density matrix (TRDM) and second, the computational complexity scales linearly with the number of the reference states. The extended multistate (XMS) treatment is further incorporated, giving suited treatment of the zeroth-order Hamiltonian despite the fact that the SS-SR based IC basis is not invariant with respect to the XMS rotation. In addition, the state-specific fourth-order reduced density matrix (RDM) is eliminated in an approximate fashion using the cumulant reconstruction formula, as also done in the previous state-specific DMRG-cu(4)-CASPT2 approach. The resultant method, referred to as DMRG-cu(4)-XMS-CASPT2, uses the RDMs and TRDMs of up to third-order provided by the DMRG calculation. The multistate potential energy curves of the photoisomerization of diarylethene derivatives with CAS(26e,24o) are presented to illustrate the applicability of our theoretical approach.

リンク情報
DOI
https://doi.org/10.1021/acs.jctc.7b00735
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000412965700019&DestApp=WOS_CPL
ID情報
  • DOI : 10.1021/acs.jctc.7b00735
  • ISSN : 1549-9618
  • eISSN : 1549-9626
  • Web of Science ID : WOS:000412965700019

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