TY - JOUR
T1 - Benchmark of density functional theory methods for the study of organic polysulfides
AU - Sharma, Jyoti
AU - Champagne, Pier Alexandre
N1 - Funding Information:
This work was funded by the American Chemical Society Petroleum Research Fund (ACS PRF, grant # 61891‐DNI4). Startup funds from the New Jersey Institute and Technology (NJIT) are gratefully acknowledged. Calculations for this work were performed on the Kong and Lochness clusters at NJIT. The authors are grateful to ChemRxiv for hosting this manuscript as a pre‐print ( https://doi.org/10.26434/chemrxiv-2022-r7fgp ).
Funding Information:
American Chemical Society Petroleum Research Fund, Grant/Award Number: 61891‐DNI4; New Jersey Institute and Technology (NJIT) Funding information
Publisher Copyright:
© 2022 Wiley Periodicals LLC.
PY - 2022/12/15
Y1 - 2022/12/15
N2 - Elemental sulfur is often used in organic synthesis as its low cost and high abundance make it a highly desirable source of sulfur atoms. However, sulfur's unpredictable catenation behavior poses challenges to its widespread usage due to difficulties in designing new reactions that can account for its multifaceted reactivity. In order to accurately model sulfur's mechanisms using computational approaches, it is necessary to identify density functional theory (DFT) methods that are accurate on these systems. This study benchmarks 12 well-known DFT functionals that include local, non-local, and hybrid methods against DLPNO-CCSD(T)/aug-cc-pV(Q+d)Z//MP2/aug-cc-pV(T+d)Z/SMD(MeCN) for the accurate treatment of organic polysulfides, taking cyanide as a nucleophile. Our benchmarking results indicate that the M06-2X and B3LYP-D3(BJ) density functionals are the most accurate for calculating reaction energies, while local functionals performed the worst. For activation energies, MN15, MN15-L, M06-2X, and ωB97X-D are the most accurate. Our analysis of structural parameters shows that all functionals perform well for ground state optimizations except B97D3, while MN15-L and M06-2X performed best for transition structure optimizations. Overall, the four hybrid functionals MN15, M06-2X, ωB97X-D, and B3LYP-D3(BJ) appear adequate for studying the reaction mechanisms of polysulfides.
AB - Elemental sulfur is often used in organic synthesis as its low cost and high abundance make it a highly desirable source of sulfur atoms. However, sulfur's unpredictable catenation behavior poses challenges to its widespread usage due to difficulties in designing new reactions that can account for its multifaceted reactivity. In order to accurately model sulfur's mechanisms using computational approaches, it is necessary to identify density functional theory (DFT) methods that are accurate on these systems. This study benchmarks 12 well-known DFT functionals that include local, non-local, and hybrid methods against DLPNO-CCSD(T)/aug-cc-pV(Q+d)Z//MP2/aug-cc-pV(T+d)Z/SMD(MeCN) for the accurate treatment of organic polysulfides, taking cyanide as a nucleophile. Our benchmarking results indicate that the M06-2X and B3LYP-D3(BJ) density functionals are the most accurate for calculating reaction energies, while local functionals performed the worst. For activation energies, MN15, MN15-L, M06-2X, and ωB97X-D are the most accurate. Our analysis of structural parameters shows that all functionals perform well for ground state optimizations except B97D3, while MN15-L and M06-2X performed best for transition structure optimizations. Overall, the four hybrid functionals MN15, M06-2X, ωB97X-D, and B3LYP-D3(BJ) appear adequate for studying the reaction mechanisms of polysulfides.
KW - benchmark
KW - density functional theory
KW - elemental sulfur and polysulfides
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U2 - 10.1002/jcc.27007
DO - 10.1002/jcc.27007
M3 - Article
C2 - 36169869
AN - SCOPUS:85139076999
SN - 0192-8651
VL - 43
SP - 2131
EP - 2138
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
IS - 32
ER -