Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 13, Issue 10, Pages 4829-4840Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.7b00735
Keywords
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Funding
- JSPS KAKENHI [JP15H01097, JP16H04101, JP17H05274]
- National Natural Science Foundation of China [21501189]
- Grant Agency of the Czech Republic [15-19143S]
- [L16525]
- Grants-in-Aid for Scientific Research [16H04101, 17H05274] Funding Source: KAKEN
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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.
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