Chemical Bonding in Three-Membered Ring Systems
The formation of the four 3-ring systems c-(CH<sub>2</sub>)<sub>3−<i>k</i></sub>(SiH<sub>2</sub>)<sub><i>k</i></sub> (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"...
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2025-01-01
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| author | Nina Strasser Alexander F. Sax |
| author_facet | Nina Strasser Alexander F. Sax |
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| description | The formation of the four 3-ring systems c-(CH<sub>2</sub>)<sub>3−<i>k</i></sub>(SiH<sub>2</sub>)<sub><i>k</i></sub> (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>k</mi><mo>=</mo><mn>0</mn></mrow></semantics></math></inline-formula>: cyclopropane, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>k</mi><mo>=</mo><mn>1</mn></mrow></semantics></math></inline-formula>: silirane, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>k</mi><mo>=</mo><mn>2</mn></mrow></semantics></math></inline-formula>: disilirane, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>k</mi><mo>=</mo><mn>3</mn></mrow></semantics></math></inline-formula>: cyclotrisilane) by addition of methylene and silylene to the double bond in ethene, disilene, and silaethene, as well as the elimination of the carbene analogs from the 3-rings, was studied with CAS(4,4) wave functions in both <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mrow><mn>2</mn><mi>v</mi></mrow></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mi>s</mi></msub></semantics></math></inline-formula> symmetry. To reveal the charge and spin redistribution during these reactions the CAS(4,4) wave functions were analyzed using the orthogonal valence bond method (OVB). The potential energy curves, different internal coordinates, and the results of the OVB analysis show that, frequently, the addition and elimination reactions follow different minimum energy paths, because they are indeed diabatic reactions. In these cases, there are no energy barriers corresponding to saddle points on the potential energy surfaces but the energy increases during one diabatic reaction until, at a certain point, the system jumps to the other diabatic state and, in the following, the energy decreases. This happens for reactions in <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mrow><mn>2</mn><mi>v</mi></mrow></msub></semantics></math></inline-formula> symmetry; as soon as the system can change to the lower symmetry, the diabatic states combine to an adiabatic one and the reaction follows a single minimum energy path. |
| format | Article |
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| publishDate | 2025-01-01 |
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| spelling | doaj-art-cdda011b93434147bc8baa31f3bc27cf2025-08-20T02:48:07ZengMDPI AGMolecules1420-30492025-01-0130361210.3390/molecules30030612Chemical Bonding in Three-Membered Ring SystemsNina Strasser0Alexander F. Sax1Institute of Solid State Physics, Graz University of Technology, Petersgasse 16, 8010 Graz, AustriaDepartment of Chemistry, University of Graz, Heinrichstrasse 28, 8010 Graz, AustriaThe formation of the four 3-ring systems c-(CH<sub>2</sub>)<sub>3−<i>k</i></sub>(SiH<sub>2</sub>)<sub><i>k</i></sub> (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>k</mi><mo>=</mo><mn>0</mn></mrow></semantics></math></inline-formula>: cyclopropane, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>k</mi><mo>=</mo><mn>1</mn></mrow></semantics></math></inline-formula>: silirane, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>k</mi><mo>=</mo><mn>2</mn></mrow></semantics></math></inline-formula>: disilirane, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>k</mi><mo>=</mo><mn>3</mn></mrow></semantics></math></inline-formula>: cyclotrisilane) by addition of methylene and silylene to the double bond in ethene, disilene, and silaethene, as well as the elimination of the carbene analogs from the 3-rings, was studied with CAS(4,4) wave functions in both <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mrow><mn>2</mn><mi>v</mi></mrow></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mi>s</mi></msub></semantics></math></inline-formula> symmetry. To reveal the charge and spin redistribution during these reactions the CAS(4,4) wave functions were analyzed using the orthogonal valence bond method (OVB). The potential energy curves, different internal coordinates, and the results of the OVB analysis show that, frequently, the addition and elimination reactions follow different minimum energy paths, because they are indeed diabatic reactions. In these cases, there are no energy barriers corresponding to saddle points on the potential energy surfaces but the energy increases during one diabatic reaction until, at a certain point, the system jumps to the other diabatic state and, in the following, the energy decreases. This happens for reactions in <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>C</mi><mrow><mn>2</mn><mi>v</mi></mrow></msub></semantics></math></inline-formula> symmetry; as soon as the system can change to the lower symmetry, the diabatic states combine to an adiabatic one and the reaction follows a single minimum energy path.https://www.mdpi.com/1420-3049/30/3/612CASSCFlocalized orbitalsorthogonal valence bondeliminationrecombinationdiabatic reaction |
| spellingShingle | Nina Strasser Alexander F. Sax Chemical Bonding in Three-Membered Ring Systems Molecules CASSCF localized orbitals orthogonal valence bond elimination recombination diabatic reaction |
| title | Chemical Bonding in Three-Membered Ring Systems |
| title_full | Chemical Bonding in Three-Membered Ring Systems |
| title_fullStr | Chemical Bonding in Three-Membered Ring Systems |
| title_full_unstemmed | Chemical Bonding in Three-Membered Ring Systems |
| title_short | Chemical Bonding in Three-Membered Ring Systems |
| title_sort | chemical bonding in three membered ring systems |
| topic | CASSCF localized orbitals orthogonal valence bond elimination recombination diabatic reaction |
| url | https://www.mdpi.com/1420-3049/30/3/612 |
| work_keys_str_mv | AT ninastrasser chemicalbondinginthreememberedringsystems AT alexanderfsax chemicalbondinginthreememberedringsystems |