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

Yanai, Takeshi and Saitow, Masaaki and Xiong, Xiao-Gen and Chalupský, Jakub and Kurashige, Yuki and Guo, Sheng and Sharma, Sandeep (2017) Multistate Complete-Active-Space Second-Order Perturbation Theory Based on Density Matrix Renormalization Group Reference States. Journal of Chemical Theory and Computation, 13 (10). pp. 4829-4840. ISSN 1549-9618. http://resolver.caltech.edu/CaltechAUTHORS:20170914-110138411

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Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jctc.7b00735DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.jctc.7b00735PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.jctc.7b00735PublisherSupporting Information
ORCID:
AuthorORCID
Kurashige, Yuki0000-0003-4652-8153
Guo, Sheng0000-0002-1083-1882
Sharma, Sandeep0000-0002-6598-8887
Additional Information:© 2017 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: July 10, 2017; Published: September 7, 2017. This work was supported partially by JSPS KAKENHI Grant Nos. JP15H01097, JP16H04101, and JP17H05274 for T.Y. and National Natural Science Foundation of China (21501189) and Grant-in-Aid for Invitational Fellowship for Research in Japan (L16525) for X.-G.X. J.Ch. was supported by the Grant Agency of the Czech Republic (Grant No. 15-19143S) and institutional support RVO 61388963 (CAS). The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)JP15H01097
Japan Society for the Promotion of Science (JSPS)JP16H04101
Japan Society for the Promotion of Science (JSPS)JP17H05274
National Natural Science Foundation of China21501189
Japan Society for the Promotion of Science (JSPS)L16525
Grant Agency of the Czech Republic15-19143S
Grant Agency of the Czech RepublicRVO 61388963
Record Number:CaltechAUTHORS:20170914-110138411
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170914-110138411
Official Citation:Multistate Complete-Active-Space Second-Order Perturbation Theory Based on Density Matrix Renormalization Group Reference States Takeshi Yanai, Masaaki Saitow, Xiao-Gen Xiong, Jakub Chalupský, Yuki Kurashige, Sheng Guo, and Sandeep Sharma Journal of Chemical Theory and Computation 2017 13 (10), 4829-4840 DOI: 10.1021/acs.jctc.7b00735
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:81441
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:14 Sep 2017 18:11
Last Modified:22 Mar 2019 20:56

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