Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 17, Issue 3, Pages 1497-1511Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.0c01231
Keywords
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Funding
- National Natural Science Foundation of China Young Scientist Fund [21603145]
- National Natural Science Foundation of China International Young Scientist Fund [21750110439, 21851110758]
- NYU-ECNU Center for Computational Chemistry
- NYU Shanghai
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The study investigates the convergence of the many-body expansion for a prototypical hole-transfer reaction between Zn(0) and Zn(I) in a condensed-phase environment. By using a charge-localized representation of the electronic Hamiltonian, a diabatic many-body expansion method is introduced for ground- and excited-state potential energy surfaces of a charge-transfer reaction. This approach, combined with a multiconfigurational self-consistent field, provides a fragmentation method that scales quadratically with system size while maintaining chemical accuracy compared to full system calculations.
We explore the convergence of the many-body expansion for a prototypical hole-transfer reaction between Zn(0) and Zn(I) in a condensed-phase environment. Poor convergence of state energies is seen when the adiabatic representation is used, which can be understood from the fragment single-point calculations at low orders of the many-body expansion incorrectly localizing charges compared to the full system, thus leading to qualitative errors in the electronic structure of the adiabatic states between fragments. Using a charge-localized representation of the electronic Hamiltonian, we introduce a diabatic many-body expansion method with quantitative accuracy for ground- and excited-state potential energy surfaces of a charge-transfer reaction. Combining with a multiconfigurational self-consistent field affords a fragmentation approach that scales quadratically with system size while retaining chemical accuracy (<1 kcal/mol) in total energies compared to full system calculations.
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