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Combining Internally Contracted States and Matrix Product States To Perform Multireference Perturbation Theory.

Accepted version
Peer-reviewed

Type

Article

Change log

Authors

Knizia, Gerald 
Guo, Sheng 
Alavi, Ali 

Abstract

We present two efficient and intruder-free methods for treating dynamic correlation on top of general multiconfiguration reference wave functions - including such as obtained by the density matrix renormalization group (DMRG) with large active spaces. The new methods are the second order variant of the recently proposed multireference linearized coupled cluster method (MRLCC) [ Sharma, S.; Alavi, A. J. Chem. Phys. 2015 , 143 , 102815 ] and of N-electron valence perturbation theory (NEVPT2), with expected accuracies similar to MRCI+Q and (at least) CASPT2, respectively. Great efficiency gains are realized by representing the first order wave function with a combination of internal contraction (IC) and matrix product state perturbation theory (MPSPT). With this combination, only third order reduced density matrices (RDMs) are required. Thus, we obviate the need for calculating (or estimating) RDMs of fourth or higher order; these had so far posed a severe bottleneck for dynamic correlation treatments involving the large active spaces accessible to DMRG. Using several benchmark systems, including first and second row containing small molecules, Cr2, pentacene, and oxo-Mn(Salen), we show that active spaces containing at least 30 orbitals can be treated using this method. On a single node, MRLCC2 and NEVPT2 calculations can be performed with over 550 and 1100 virtual orbitals, respectively. We also critically examine the errors incurred due to the three sources of errors introduced in the present implementation - calculating second order instead of third order energy corrections, use of internal contraction, and approximations made in the reference wave function due to DMRG.

Description

Keywords

0101 Pure Mathematics

Journal Title

J Chem Theory Comput

Conference Name

Journal ISSN

1549-9618
1549-9626

Volume Title

13

Publisher

American Chemical Society (ACS)