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      Quantification of the Helicality of Helical Molecular Orbitals

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          Abstract

          The frontier molecular orbital (MO) topology of linear carbon molecules, such as polyynes, can be visually identified as helices. However, there is no clear way to quantify the helical curvature of these π-MOs, and it is thus challenging to quantify correlations between the helical curvature and molecular properties. In this paper, we develop a method that enables us to compute the helical curvature of MOs based on their nodal planes. Using this method, we define a robust way of quantifying the helical nature of MOs (helicality) by their deviation from a perfect helix. We explore several limiting cases, including polyynes, metallacumulenes, cyclic allenes, and spiroconjugated systems, where the change in helical curvature is subtle yet clearly highlighted with this method. For example, we show that strain only has a minor effect on the helicality of the frontier orbitals of cycloallenes and that the MOs of spiroconjugated systems are close to perfect helices around the spiro-carbon. Our work provides a well-defined method for assessing orbital helicality beyond visual inspection of MO isosurfaces, thus paving the way for future studies of how the helicality of π-MOs affects molecular properties.

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            Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon

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              Energy-adjustedab initio pseudopotentials for the second and third row transition elements

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                Author and article information

                Journal
                J Phys Chem A
                J Phys Chem A
                jx
                jpcafh
                The Journal of Physical Chemistry. a
                American Chemical Society
                1089-5639
                1520-5215
                07 September 2021
                16 September 2021
                : 125
                : 36
                : 8107-8115
                Affiliations
                Department of Chemistry and Nano-Science Center, University of Copenhagen , Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark
                Author notes
                Article
                10.1021/acs.jpca.1c05799
                8450904
                34491758
                © 2021 The Authors. Published by American Chemical Society

                Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works ( https://creativecommons.org/licenses/by-nc-nd/4.0/).

                Funding
                Funded by: H2020 European Research Council, doi 10.13039/100010663;
                Award ID: 865870
                Categories
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                Custom metadata
                jp1c05799
                jp1c05799

                Physical chemistry

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