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Performance of Electronic Structure Methods for the Description of Hückel–Möbius Interconversions in Extended π-Systems
[Image: see text] Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. DFT remains the workhorse for modeling such extended macrocycles, when taking into account their size an...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2020
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7307915/ https://www.ncbi.nlm.nih.gov/pubmed/32093467 http://dx.doi.org/10.1021/acs.jpca.9b10880 |
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author | Woller, Tatiana Banerjee, Ambar Sylvetsky, Nitai Santra, Golokesh Deraet, Xavier De Proft, Frank Martin, Jan M. L. Alonso, Mercedes |
author_facet | Woller, Tatiana Banerjee, Ambar Sylvetsky, Nitai Santra, Golokesh Deraet, Xavier De Proft, Frank Martin, Jan M. L. Alonso, Mercedes |
author_sort | Woller, Tatiana |
collection | PubMed |
description | [Image: see text] Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. DFT remains the workhorse for modeling such extended macrocycles, when taking into account their size and huge conformational flexibility. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, π···π stacking, steric effects, ring strain, and electron delocalization. As a consequence, the selection of an exchange–correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wave function methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a stronger degree of static correlation than the Hückel and twisted-Hückel structures, and as a result the relative energies of singly twisted structures are a challenging test for electronic structure methods. Comparison of limited orbital space full CI calculations with CCSD(T) calculations within the same active spaces shows that post-CCSD(T) correlation contributions to relative energies are very minor. At the same time, relative energies are weakly sensitive to further basis set expansion, as proven by the minor energy differences between the extrapolated MP2/CBS energies estimated from cc-pV{T,Q}Z, diffuse-augmented heavy-aug-cc-pV{T,Q}Z and explicitly correlated MP2-F12/cc-pVDZ-F12 calculations. Hence, our CCSD(T) reference values are reasonably well-converged in both 1-particle and n-particle spaces. While conventional MP2 and MP3 yield very poor results, SCS-MP2 and particularly SOS-MP2 and SCS-MP3 agree to better than 1 kcal mol(–1) with the CCSD(T) relative energies. Regarding DFT methods, the range-separated double hybrids, such as ωB97M(2) and B2GP-PLYP, outperform other functionals with RMSDs of 0.6 and 0.8 kcal mol(–1), respectively. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended π-systems, the errors drop down to 1.9 kcal mol(–1) for the revised revDOD-PBEP86-NL, which eliminates the same-spin correlation energy. Minnesota meta-GGA functionals with high fractions of exact exchange (M06-2X and M08-HX) also perform reasonably well, outperforming more robust and significantly less empirically parametrized functionals like SCAN0-D3. |
format | Online Article Text |
id | pubmed-7307915 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-73079152020-06-23 Performance of Electronic Structure Methods for the Description of Hückel–Möbius Interconversions in Extended π-Systems Woller, Tatiana Banerjee, Ambar Sylvetsky, Nitai Santra, Golokesh Deraet, Xavier De Proft, Frank Martin, Jan M. L. Alonso, Mercedes J Phys Chem A [Image: see text] Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. DFT remains the workhorse for modeling such extended macrocycles, when taking into account their size and huge conformational flexibility. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, π···π stacking, steric effects, ring strain, and electron delocalization. As a consequence, the selection of an exchange–correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wave function methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a stronger degree of static correlation than the Hückel and twisted-Hückel structures, and as a result the relative energies of singly twisted structures are a challenging test for electronic structure methods. Comparison of limited orbital space full CI calculations with CCSD(T) calculations within the same active spaces shows that post-CCSD(T) correlation contributions to relative energies are very minor. At the same time, relative energies are weakly sensitive to further basis set expansion, as proven by the minor energy differences between the extrapolated MP2/CBS energies estimated from cc-pV{T,Q}Z, diffuse-augmented heavy-aug-cc-pV{T,Q}Z and explicitly correlated MP2-F12/cc-pVDZ-F12 calculations. Hence, our CCSD(T) reference values are reasonably well-converged in both 1-particle and n-particle spaces. While conventional MP2 and MP3 yield very poor results, SCS-MP2 and particularly SOS-MP2 and SCS-MP3 agree to better than 1 kcal mol(–1) with the CCSD(T) relative energies. Regarding DFT methods, the range-separated double hybrids, such as ωB97M(2) and B2GP-PLYP, outperform other functionals with RMSDs of 0.6 and 0.8 kcal mol(–1), respectively. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended π-systems, the errors drop down to 1.9 kcal mol(–1) for the revised revDOD-PBEP86-NL, which eliminates the same-spin correlation energy. Minnesota meta-GGA functionals with high fractions of exact exchange (M06-2X and M08-HX) also perform reasonably well, outperforming more robust and significantly less empirically parametrized functionals like SCAN0-D3. American Chemical Society 2020-02-24 2020-03-26 /pmc/articles/PMC7307915/ /pubmed/32093467 http://dx.doi.org/10.1021/acs.jpca.9b10880 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Woller, Tatiana Banerjee, Ambar Sylvetsky, Nitai Santra, Golokesh Deraet, Xavier De Proft, Frank Martin, Jan M. L. Alonso, Mercedes Performance of Electronic Structure Methods for the Description of Hückel–Möbius Interconversions in Extended π-Systems |
title | Performance of Electronic Structure Methods for the
Description of Hückel–Möbius Interconversions
in Extended π-Systems |
title_full | Performance of Electronic Structure Methods for the
Description of Hückel–Möbius Interconversions
in Extended π-Systems |
title_fullStr | Performance of Electronic Structure Methods for the
Description of Hückel–Möbius Interconversions
in Extended π-Systems |
title_full_unstemmed | Performance of Electronic Structure Methods for the
Description of Hückel–Möbius Interconversions
in Extended π-Systems |
title_short | Performance of Electronic Structure Methods for the
Description of Hückel–Möbius Interconversions
in Extended π-Systems |
title_sort | performance of electronic structure methods for the
description of hückel–möbius interconversions
in extended π-systems |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7307915/ https://www.ncbi.nlm.nih.gov/pubmed/32093467 http://dx.doi.org/10.1021/acs.jpca.9b10880 |
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