Reaction barrier heights for cycloreversion of heterocyclic rings: An Achilles' heel for DFT and standard ab initio procedures

Li Juan Yu; Farzaneh Sarrami; Robert J. O'Reilly; Amir Karton

doi:10.1016/j.chemphys.2015.07.005

Reaction barrier heights for cycloreversion of heterocyclic rings: An Achilles' heel for DFT and standard ab initio procedures

Li Juan Yu, Farzaneh Sarrami, Robert J. O'Reilly, Amir Karton

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

41 Citations (Scopus)

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	https://doi.org/10.1016/j.chemphys.2015.07.005
Publication status	Published - Jul 21 2015

Keywords

Cycloelimination
Cycloreversion
Density functional theory
G4 theory
W1 theory

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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title = "Reaction barrier heights for cycloreversion of heterocyclic rings: An Achilles' heel for DFT and standard ab initio procedures",

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.",

keywords = "Cycloelimination, Cycloreversion, Density functional theory, G4 theory, W1 theory",

author = "Yu, {Li Juan} and Farzaneh Sarrami and O'Reilly, {Robert J.} and Amir Karton",

note = "Funding Information: Dedicated to the lifetime achievements and memory of Professor Tom Ziegler. This research was undertaken with the assistance of resources from the National Computational Infrastructure (NCI), which is supported by the Australian Government. We gratefully acknowledge the system administration support provided by the Faculty of Science at UWA to the Linux cluster of the Karton group, the provision of an Australian Postgraduate Award (to L-J.Y.), and an Australian Research Council (ARC) Discovery Early Career Researcher Award (to A.K., project number: DE140100311). ",

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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

N1 - Funding Information: Dedicated to the lifetime achievements and memory of Professor Tom Ziegler. This research was undertaken with the assistance of resources from the National Computational Infrastructure (NCI), which is supported by the Australian Government. We gratefully acknowledge the system administration support provided by the Faculty of Science at UWA to the Linux cluster of the Karton group, the provision of an Australian Postgraduate Award (to L-J.Y.), and an Australian Research Council (ARC) Discovery Early Career Researcher Award (to A.K., project number: DE140100311).

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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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Reaction barrier heights for cycloreversion of heterocyclic rings: An Achilles' heel for DFT and standard ab initio procedures

Abstract

Keywords

ASJC Scopus subject areas

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