Multilink F∗ Method for Combined Quantum Mechanical and Molecular Mechanical Calculations of Complex Systems

Research output: Contribution to journalArticle

Abstract

Combined quantum mechanical and molecular mechanical (QM/MM) studies on catalysis in metal-organic frameworks (MOFs) are relatively undeveloped in contrast to the wide use of QM/MM for enzyme catalysis. One reason is that the currently available methods for treating QM-MM boundaries are not fully compatible with the combination of features in MOFs, namely, their high connectivity, their polar bonds (e.g., metal-oxygen bonds), and their potential boundary atoms with high partial atomic charges. The treatment of polar bonds can be improved by using tuned link atoms, but both the widely used H link atom method and the F∗ link atom method provide limited options in placing the QM-MM boundary in MOFs and other covalently bonded solids, which seriously reduces the efficiency of QM/MM calculations. Here, we propose a generalized version of the F∗ link atom method with greater flexibility for the placement of the QM-MM boundary in MOFs and with a practical scheme for tuning. The new method, called the multilink F∗ method, allows a large part of an inorganic node of a MOF to be partitioned into the MM subsystem to increase the efficiency. Our validation calculations on dimerization of ethylene to 1-butene by a nickel catalyst supported on a MOF show that the overall performance of QM/MM calculations with the multilink F∗ method is excellent for energies, geometries, and partial atomic charges.

Original languageEnglish (US)
JournalJournal of Chemical Theory and Computation
DOIs
StatePublished - Jan 1 2019

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complex systems
Large scale systems
Metals
metals
Atoms
atoms
Catalysis
catalysis
Dimerization
butenes
dimerization
Nickel
Butenes
Catalyst supports
enzymes
flexibility
Ethylene
ethylene
Enzymes
Tuning

PubMed: MeSH publication types

  • Journal Article

Cite this

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title = "Multilink F∗ Method for Combined Quantum Mechanical and Molecular Mechanical Calculations of Complex Systems",
abstract = "Combined quantum mechanical and molecular mechanical (QM/MM) studies on catalysis in metal-organic frameworks (MOFs) are relatively undeveloped in contrast to the wide use of QM/MM for enzyme catalysis. One reason is that the currently available methods for treating QM-MM boundaries are not fully compatible with the combination of features in MOFs, namely, their high connectivity, their polar bonds (e.g., metal-oxygen bonds), and their potential boundary atoms with high partial atomic charges. The treatment of polar bonds can be improved by using tuned link atoms, but both the widely used H link atom method and the F∗ link atom method provide limited options in placing the QM-MM boundary in MOFs and other covalently bonded solids, which seriously reduces the efficiency of QM/MM calculations. Here, we propose a generalized version of the F∗ link atom method with greater flexibility for the placement of the QM-MM boundary in MOFs and with a practical scheme for tuning. The new method, called the multilink F∗ method, allows a large part of an inorganic node of a MOF to be partitioned into the MM subsystem to increase the efficiency. Our validation calculations on dimerization of ethylene to 1-butene by a nickel catalyst supported on a MOF show that the overall performance of QM/MM calculations with the multilink F∗ method is excellent for energies, geometries, and partial atomic charges.",
author = "Wu, {Xin Ping} and Laura Gagliardi and Truhlar, {Donald G}",
year = "2019",
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doi = "10.1021/acs.jctc.9b00274",
language = "English (US)",
journal = "Journal of Chemical Theory and Computation",
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AU - Gagliardi, Laura

AU - Truhlar, Donald G

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AB - Combined quantum mechanical and molecular mechanical (QM/MM) studies on catalysis in metal-organic frameworks (MOFs) are relatively undeveloped in contrast to the wide use of QM/MM for enzyme catalysis. One reason is that the currently available methods for treating QM-MM boundaries are not fully compatible with the combination of features in MOFs, namely, their high connectivity, their polar bonds (e.g., metal-oxygen bonds), and their potential boundary atoms with high partial atomic charges. The treatment of polar bonds can be improved by using tuned link atoms, but both the widely used H link atom method and the F∗ link atom method provide limited options in placing the QM-MM boundary in MOFs and other covalently bonded solids, which seriously reduces the efficiency of QM/MM calculations. Here, we propose a generalized version of the F∗ link atom method with greater flexibility for the placement of the QM-MM boundary in MOFs and with a practical scheme for tuning. The new method, called the multilink F∗ method, allows a large part of an inorganic node of a MOF to be partitioned into the MM subsystem to increase the efficiency. Our validation calculations on dimerization of ethylene to 1-butene by a nickel catalyst supported on a MOF show that the overall performance of QM/MM calculations with the multilink F∗ method is excellent for energies, geometries, and partial atomic charges.

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