期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 122, 期 22, 页码 4988-4996出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.8b00941
关键词
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资金
- United States National Science Foundation [CHE-1565638]
- United States Army Research Office (ARO) [W911NF-16-C-0030, W911NF-16-1-0152]
- United States Air Force Office of Scientific Research Grant [FA9550-14-1-0367]
FeMoco, MoFe7S9C, has been shown to be the active catalytic site for the reduction of nitrogen to ammonia in the nitrogenase protein. An understanding of its electronic structure including strong electron correlation is key to designing mimic catalysts capable of ambient nitrogen fixation. Active spaces ranging from [54, 54] to [65, 57] have been predicted for a quantitative description of FeMoco's electronic structure. However, a wave function approach for a singlet state using a [54, 54] active space would require 1029 variables. In this work, we systematically explore the active-space size necessary to qualitatively capture strong correlation in FeMoco and two related moieties, MoFe3S7 and Fe4S7. Using CASSCF and 2-RDM methods, we consider active-space sizes up to [14, 14] and [30, 30], respectively, with STO-3G, 3-21G, and DZP basis sets and use fractional natural-orbital occupation numbers to assess the level of multireference electron correlation, an examination of which reveals a competition between single-reference and multi reference solutions to the electronic Schrodinger equation for smaller active spaces and a consistent multi reference solution for larger active spaces.
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