Bader’s Topological Bond Path Does Not Necessarily Indicate Stabilizing Interaction—Proof Studies Based on the Ng@[3<sub>n</sub>]cyclophane Endohedral Complexes
According to Bader’s quantum theory of atoms in molecules (QTAIM), the simultaneous presence of a bond path and the corresponding bond critical point between any two atoms is both a necessary and sufficient condition for the atoms to be bonded to one another. In principle, this means that this pair...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-08-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/17/6353 |
| _version_ | 1797582140960931840 |
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| author | Mirosław Jabłoński |
| author_facet | Mirosław Jabłoński |
| author_sort | Mirosław Jabłoński |
| collection | DOAJ |
| description | According to Bader’s quantum theory of atoms in molecules (QTAIM), the simultaneous presence of a bond path and the corresponding bond critical point between any two atoms is both a necessary and sufficient condition for the atoms to be bonded to one another. In principle, this means that this pair of atoms should make a stabilizing contribution to the molecular system. However, the multitude of so-called counterintuitive bond paths strongly suggests that this statement is not necessarily true. Particularly ‘troublesome’ are endohedral complexes, in which encapsulation-enforced proximity between the trapped guest (e.g., an atom) and the host’s cage system usually ‘produces’ many counterintuitive bond paths. In the author’s opinion, the best evidence to demonstrate the repulsive nature of the intra-cage guest⋯host interaction is the use of some trapping systems containing small escape channels and then showing that the initially trapped entity spontaneously escapes outside the host’s cage during geometry optimization of the initially built guest@host endohedral complex. For this purpose, a group of 24 Ng@[3<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>n</mi></msub></semantics></math></inline-formula>]cyclophane (3<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>≤</mo><mi>n</mi><mo>≤</mo></mrow></semantics></math></inline-formula>6) endohedral complexes is used. As a result, arguments are presented showing that Bader’s topological bond path does not necessarily indicate a stabilizing interaction. |
| first_indexed | 2024-03-10T23:16:42Z |
| format | Article |
| id | doaj.art-ba91fdb8337a44ec9f1cb0bb06cce1da |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T23:16:42Z |
| publishDate | 2023-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-ba91fdb8337a44ec9f1cb0bb06cce1da2023-11-19T08:34:49ZengMDPI AGMolecules1420-30492023-08-012817635310.3390/molecules28176353Bader’s Topological Bond Path Does Not Necessarily Indicate Stabilizing Interaction—Proof Studies Based on the Ng@[3<sub>n</sub>]cyclophane Endohedral ComplexesMirosław Jabłoński0Faculty of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87-100 Toruń, PolandAccording to Bader’s quantum theory of atoms in molecules (QTAIM), the simultaneous presence of a bond path and the corresponding bond critical point between any two atoms is both a necessary and sufficient condition for the atoms to be bonded to one another. In principle, this means that this pair of atoms should make a stabilizing contribution to the molecular system. However, the multitude of so-called counterintuitive bond paths strongly suggests that this statement is not necessarily true. Particularly ‘troublesome’ are endohedral complexes, in which encapsulation-enforced proximity between the trapped guest (e.g., an atom) and the host’s cage system usually ‘produces’ many counterintuitive bond paths. In the author’s opinion, the best evidence to demonstrate the repulsive nature of the intra-cage guest⋯host interaction is the use of some trapping systems containing small escape channels and then showing that the initially trapped entity spontaneously escapes outside the host’s cage during geometry optimization of the initially built guest@host endohedral complex. For this purpose, a group of 24 Ng@[3<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>n</mi></msub></semantics></math></inline-formula>]cyclophane (3<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>≤</mo><mi>n</mi><mo>≤</mo></mrow></semantics></math></inline-formula>6) endohedral complexes is used. As a result, arguments are presented showing that Bader’s topological bond path does not necessarily indicate a stabilizing interaction.https://www.mdpi.com/1420-3049/28/17/6353superphanecyclophanenoble gas atomendohedral complexexohedral complexencapsulation |
| spellingShingle | Mirosław Jabłoński Bader’s Topological Bond Path Does Not Necessarily Indicate Stabilizing Interaction—Proof Studies Based on the Ng@[3<sub>n</sub>]cyclophane Endohedral Complexes Molecules superphane cyclophane noble gas atom endohedral complex exohedral complex encapsulation |
| title | Bader’s Topological Bond Path Does Not Necessarily Indicate Stabilizing Interaction—Proof Studies Based on the Ng@[3<sub>n</sub>]cyclophane Endohedral Complexes |
| title_full | Bader’s Topological Bond Path Does Not Necessarily Indicate Stabilizing Interaction—Proof Studies Based on the Ng@[3<sub>n</sub>]cyclophane Endohedral Complexes |
| title_fullStr | Bader’s Topological Bond Path Does Not Necessarily Indicate Stabilizing Interaction—Proof Studies Based on the Ng@[3<sub>n</sub>]cyclophane Endohedral Complexes |
| title_full_unstemmed | Bader’s Topological Bond Path Does Not Necessarily Indicate Stabilizing Interaction—Proof Studies Based on the Ng@[3<sub>n</sub>]cyclophane Endohedral Complexes |
| title_short | Bader’s Topological Bond Path Does Not Necessarily Indicate Stabilizing Interaction—Proof Studies Based on the Ng@[3<sub>n</sub>]cyclophane Endohedral Complexes |
| title_sort | bader s topological bond path does not necessarily indicate stabilizing interaction proof studies based on the ng 3 sub n sub cyclophane endohedral complexes |
| topic | superphane cyclophane noble gas atom endohedral complex exohedral complex encapsulation |
| url | https://www.mdpi.com/1420-3049/28/17/6353 |
| work_keys_str_mv | AT mirosławjabłonski baderstopologicalbondpathdoesnotnecessarilyindicatestabilizinginteractionproofstudiesbasedontheng3subnsubcyclophaneendohedralcomplexes |