Massive Assessment of the Geometries of Atmospheric Molecular Clusters

Andreas Buchgraitz Jensen; Jonas Elm

doi:10.1021/acs.jctc.4c01046

Massive Assessment of the Geometries of Atmospheric Molecular Clusters

^*Corresponding author for this work

Department of Chemistry

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Abstract

Atmospheric molecular clusters are important for the formation of new aerosol particles in the air. However, current experimental techniques are not able to yield direct insight into the cluster geometries. This implies that to date there is limited information about how accurately the applied computational methods depict the cluster structures. Here we massively benchmark the molecular geometries of atmospheric molecular clusters. We initially assessed how well different DF-MP2 approaches reproduce the geometries of 45 dimer clusters obtained at a high DF-CCSD(T)-F12b/cc-pVDZ-F12 level of theory. Based on the results, we find that the DF-MP2/aug-cc-pVQZ level of theory best resembles the DF-CCSD(T)-F12b/cc-pVDZ-F12 reference level. We subsequently optimized 1283 acid-base cluster structures (up to tetramers) at the DF-MP2/aug-cc-pVQZ level of theory and assessed how more approximate methods reproduce the geometries. Out of the tested semiempirical methods, we find that the newly parametrized atmospheric molecular cluster extended tight binding method (AMC-xTB) is most reliable for locating the correct lowest energy configuration and yields the lowest root mean square deviation (RMSD) compared to the reference level. In addition, we find that the DFT-3c methods show similar performance as the usually employed ωB97X-D/6-31++G(d,p) level of theory at a potentially reduced computational cost. This suggests that these methods could prove to be valuable for large-scale screening of cluster structures in the future.

Original language	English
Journal	Journal of Chemical Theory and Computation
Volume	20
Issue	19
Pages (from-to)	8549–8558
Number of pages	10
ISSN	1549-9618
DOIs	https://doi.org/10.1021/acs.jctc.4c01046
Publication status	Published - 8 Oct 2024

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10.1021/acs.jctc.4c01046

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title = "Massive Assessment of the Geometries of Atmospheric Molecular Clusters",

abstract = "Atmospheric molecular clusters are important for the formation of new aerosol particles in the air. However, current experimental techniques are not able to yield direct insight into the cluster geometries. This implies that to date there is limited information about how accurately the applied computational methods depict the cluster structures. Here we massively benchmark the molecular geometries of atmospheric molecular clusters. We initially assessed how well different DF-MP2 approaches reproduce the geometries of 45 dimer clusters obtained at a high DF-CCSD(T)-F12b/cc-pVDZ-F12 level of theory. Based on the results, we find that the DF-MP2/aug-cc-pVQZ level of theory best resembles the DF-CCSD(T)-F12b/cc-pVDZ-F12 reference level. We subsequently optimized 1283 acid-base cluster structures (up to tetramers) at the DF-MP2/aug-cc-pVQZ level of theory and assessed how more approximate methods reproduce the geometries. Out of the tested semiempirical methods, we find that the newly parametrized atmospheric molecular cluster extended tight binding method (AMC-xTB) is most reliable for locating the correct lowest energy configuration and yields the lowest root mean square deviation (RMSD) compared to the reference level. In addition, we find that the DFT-3c methods show similar performance as the usually employed ωB97X-D/6-31++G(d,p) level of theory at a potentially reduced computational cost. This suggests that these methods could prove to be valuable for large-scale screening of cluster structures in the future.",

author = "Jensen, {Andreas Buchgraitz} and Jonas Elm",

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N2 - Atmospheric molecular clusters are important for the formation of new aerosol particles in the air. However, current experimental techniques are not able to yield direct insight into the cluster geometries. This implies that to date there is limited information about how accurately the applied computational methods depict the cluster structures. Here we massively benchmark the molecular geometries of atmospheric molecular clusters. We initially assessed how well different DF-MP2 approaches reproduce the geometries of 45 dimer clusters obtained at a high DF-CCSD(T)-F12b/cc-pVDZ-F12 level of theory. Based on the results, we find that the DF-MP2/aug-cc-pVQZ level of theory best resembles the DF-CCSD(T)-F12b/cc-pVDZ-F12 reference level. We subsequently optimized 1283 acid-base cluster structures (up to tetramers) at the DF-MP2/aug-cc-pVQZ level of theory and assessed how more approximate methods reproduce the geometries. Out of the tested semiempirical methods, we find that the newly parametrized atmospheric molecular cluster extended tight binding method (AMC-xTB) is most reliable for locating the correct lowest energy configuration and yields the lowest root mean square deviation (RMSD) compared to the reference level. In addition, we find that the DFT-3c methods show similar performance as the usually employed ωB97X-D/6-31++G(d,p) level of theory at a potentially reduced computational cost. This suggests that these methods could prove to be valuable for large-scale screening of cluster structures in the future.

AB - Atmospheric molecular clusters are important for the formation of new aerosol particles in the air. However, current experimental techniques are not able to yield direct insight into the cluster geometries. This implies that to date there is limited information about how accurately the applied computational methods depict the cluster structures. Here we massively benchmark the molecular geometries of atmospheric molecular clusters. We initially assessed how well different DF-MP2 approaches reproduce the geometries of 45 dimer clusters obtained at a high DF-CCSD(T)-F12b/cc-pVDZ-F12 level of theory. Based on the results, we find that the DF-MP2/aug-cc-pVQZ level of theory best resembles the DF-CCSD(T)-F12b/cc-pVDZ-F12 reference level. We subsequently optimized 1283 acid-base cluster structures (up to tetramers) at the DF-MP2/aug-cc-pVQZ level of theory and assessed how more approximate methods reproduce the geometries. Out of the tested semiempirical methods, we find that the newly parametrized atmospheric molecular cluster extended tight binding method (AMC-xTB) is most reliable for locating the correct lowest energy configuration and yields the lowest root mean square deviation (RMSD) compared to the reference level. In addition, we find that the DFT-3c methods show similar performance as the usually employed ωB97X-D/6-31++G(d,p) level of theory at a potentially reduced computational cost. This suggests that these methods could prove to be valuable for large-scale screening of cluster structures in the future.

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Massive Assessment of the Geometries of Atmospheric Molecular Clusters

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