期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 15, 期 1, 页码 290-302出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.8b00988
关键词
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资金
- Army Research Office Small Business Technology Transfer (STTR) program [W911NF-16-C-0124]
Complete active space self-consistent field (CASSCF) computations can be realized at polynomial cost via the variational optimization of the active-space two-electron reduced-density matrix (2-RDM). Like conventional approaches to CASSCF, variational 2-RDM (v2RDM) driven CASSCF captures nondynamical electron correlation in the active space, but it lacks a description of the remaining dynamical correlation effects. Such effects can be modeled through a combination of v2RDM-CASSCF and on-top pair-density functional theory (PDFT). The resulting v2RDM-CASSCF-PDFT approach provides a computationally inexpensive framework for describing both static and dynamical correlation effects in multiconfigurational and strongly correlated systems. On-top pair-density functionals can be derived from familiar Kohn-Sham exchange-correlation (XC) density functionals through the translation of the v2RDM-CASSCF reference densities [Li Manni et al. J. Chem. Theory Comput. 2014, 10, 3669-3680]. Translated and fully translated on-top PDFT versions of several common XC functionals are applied to the potential energy curves of N-2, H2O, and CN-, as well as to the singlet/triplet energy splittings in the linear polyacene series. Using v2RDM-CASSCF-PDFT and the translated PBE functional, the singlet/triplet energy splitting of an infinitely long acene molecule is estimated to be 4.87 kcal mol(-1).
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