Abstract
Abstract We introduce a database of 20 accurate cycloreversion barrier heights of 5-membered heterocyclic rings (to be known as the CRBH20 database). In these reactions, dioxazole and oxathiazole rings are fragmented to form isocyanates, isothiocyanates, and carbonyls. The reference reaction barrier heights are obtained by means of the high-level, ab initio W1-F12 and W1w thermochemical protocols. We evaluate the performance of 65 contemporary density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. The CRBH20 database represents an extremely challenging test for these methods. Most of the conventional DFT functionals (74%) result in root-mean-square deviations (RMSDs) between 10 and 81 kJ mol-1. The rest of the DFT functionals attain RMSDs = 5 - 10 kJ mol-1. Of the 12 tested DHDFT functionals, only five result in RMSDs <10 kJ mol-1. The CRBH20 dataset also proves to be a surprisingly challenging target for composite and standard ab initio procedures.
| Original language | English |
|---|---|
| Article number | 9350 |
| Pages (from-to) | 1-8 |
| Number of pages | 8 |
| Journal | Chemical Physics |
| Volume | 458 |
| DOIs | |
| Publication status | Published - Jul 21 2015 |
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Keywords
- Cycloelimination
- Cycloreversion
- Density functional theory
- G4 theory
- W1 theory
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Physics and Astronomy(all)
Cite this
Reaction barrier heights for cycloreversion of heterocyclic rings : An Achilles' heel for DFT and standard ab initio procedures. / Yu, Li Juan; Sarrami, Farzaneh; O'Reilly, Robert J.; Karton, Amir.
In: Chemical Physics, Vol. 458, 9350, 21.07.2015, p. 1-8.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Reaction barrier heights for cycloreversion of heterocyclic rings
T2 - An Achilles' heel for DFT and standard ab initio procedures
AU - Yu, Li Juan
AU - Sarrami, Farzaneh
AU - O'Reilly, Robert J.
AU - Karton, Amir
PY - 2015/7/21
Y1 - 2015/7/21
N2 - Abstract We introduce a database of 20 accurate cycloreversion barrier heights of 5-membered heterocyclic rings (to be known as the CRBH20 database). In these reactions, dioxazole and oxathiazole rings are fragmented to form isocyanates, isothiocyanates, and carbonyls. The reference reaction barrier heights are obtained by means of the high-level, ab initio W1-F12 and W1w thermochemical protocols. We evaluate the performance of 65 contemporary density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. The CRBH20 database represents an extremely challenging test for these methods. Most of the conventional DFT functionals (74%) result in root-mean-square deviations (RMSDs) between 10 and 81 kJ mol-1. The rest of the DFT functionals attain RMSDs = 5 - 10 kJ mol-1. Of the 12 tested DHDFT functionals, only five result in RMSDs <10 kJ mol-1. The CRBH20 dataset also proves to be a surprisingly challenging target for composite and standard ab initio procedures.
AB - Abstract We introduce a database of 20 accurate cycloreversion barrier heights of 5-membered heterocyclic rings (to be known as the CRBH20 database). In these reactions, dioxazole and oxathiazole rings are fragmented to form isocyanates, isothiocyanates, and carbonyls. The reference reaction barrier heights are obtained by means of the high-level, ab initio W1-F12 and W1w thermochemical protocols. We evaluate the performance of 65 contemporary density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. The CRBH20 database represents an extremely challenging test for these methods. Most of the conventional DFT functionals (74%) result in root-mean-square deviations (RMSDs) between 10 and 81 kJ mol-1. The rest of the DFT functionals attain RMSDs = 5 - 10 kJ mol-1. Of the 12 tested DHDFT functionals, only five result in RMSDs <10 kJ mol-1. The CRBH20 dataset also proves to be a surprisingly challenging target for composite and standard ab initio procedures.
KW - Cycloelimination
KW - Cycloreversion
KW - Density functional theory
KW - G4 theory
KW - W1 theory
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U2 - 10.1016/j.chemphys.2015.07.005
DO - 10.1016/j.chemphys.2015.07.005
M3 - Article
VL - 458
SP - 1
EP - 8
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
M1 - 9350
ER -