{"title":"比较计算自由基传播反应活化能和反应焓的耦合簇和复合量子化学方法","authors":"Timothy B. Huber, Ralph A. Wheeler","doi":"10.1039/d4cp03676j","DOIUrl":null,"url":null,"abstract":"Accurate determination of activation energies and reaction enthalpies is essential for understanding the propagation step in free radical polymerization, as it significantly affects polymer chain length and structure. In this study, we compare DLPNO-CCSD(T) to canonical CCSD(T) for 17 radical addition activation energies and 18 reaction enthalpies from Radom and Fischer’s test set. Additionally, we compare the computationally efficient composite methods G3(MP2)-RAD and CBS-RAD against CCSD(T)/aug-cc-pVTZ and DLPNO-CCSD(T)/CBS methods. Compared to the CCSD(T)/aug-cc-pVTZ reference, our results indicate that DLPNO-CCSD(T)/CBS with unrestricted Hartree-Fock (UHF) or UB3LYP reference orbitals and NormalPNO parameters consistently achieves chemical accuracy, with mean absolute deviations of 3.5 kJ/mol for activation energies and 1.5 kJ/mol for reaction enthalpies. Comparing the two composite methods shows that CBS-RAD agrees most closely with coupled cluster reaction enthalpies, while G3(MP2)-RAD tracks the activation energies most closely.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Comparing coupled cluster and composite quantum chemical methods for computing activation energies and reaction enthalpies of radical propagation reactions\",\"authors\":\"Timothy B. Huber, Ralph A. Wheeler\",\"doi\":\"10.1039/d4cp03676j\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Accurate determination of activation energies and reaction enthalpies is essential for understanding the propagation step in free radical polymerization, as it significantly affects polymer chain length and structure. In this study, we compare DLPNO-CCSD(T) to canonical CCSD(T) for 17 radical addition activation energies and 18 reaction enthalpies from Radom and Fischer’s test set. Additionally, we compare the computationally efficient composite methods G3(MP2)-RAD and CBS-RAD against CCSD(T)/aug-cc-pVTZ and DLPNO-CCSD(T)/CBS methods. Compared to the CCSD(T)/aug-cc-pVTZ reference, our results indicate that DLPNO-CCSD(T)/CBS with unrestricted Hartree-Fock (UHF) or UB3LYP reference orbitals and NormalPNO parameters consistently achieves chemical accuracy, with mean absolute deviations of 3.5 kJ/mol for activation energies and 1.5 kJ/mol for reaction enthalpies. Comparing the two composite methods shows that CBS-RAD agrees most closely with coupled cluster reaction enthalpies, while G3(MP2)-RAD tracks the activation energies most closely.\",\"PeriodicalId\":99,\"journal\":{\"name\":\"Physical Chemistry Chemical Physics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-10-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4cp03676j\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4cp03676j","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Comparing coupled cluster and composite quantum chemical methods for computing activation energies and reaction enthalpies of radical propagation reactions
Accurate determination of activation energies and reaction enthalpies is essential for understanding the propagation step in free radical polymerization, as it significantly affects polymer chain length and structure. In this study, we compare DLPNO-CCSD(T) to canonical CCSD(T) for 17 radical addition activation energies and 18 reaction enthalpies from Radom and Fischer’s test set. Additionally, we compare the computationally efficient composite methods G3(MP2)-RAD and CBS-RAD against CCSD(T)/aug-cc-pVTZ and DLPNO-CCSD(T)/CBS methods. Compared to the CCSD(T)/aug-cc-pVTZ reference, our results indicate that DLPNO-CCSD(T)/CBS with unrestricted Hartree-Fock (UHF) or UB3LYP reference orbitals and NormalPNO parameters consistently achieves chemical accuracy, with mean absolute deviations of 3.5 kJ/mol for activation energies and 1.5 kJ/mol for reaction enthalpies. Comparing the two composite methods shows that CBS-RAD agrees most closely with coupled cluster reaction enthalpies, while G3(MP2)-RAD tracks the activation energies most closely.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.