Tetrel Interactions from an Interacting Quantum Atoms Perspective
Tetrel bonds, the purportedly non-covalent interaction between a molecule that contains an atom of group 14 and an anion or (more generally) an atom or molecule with lone electron pairs, are under intense scrutiny. In this work, we perform an interacting quantum atoms (IQA) analysis of several simpl...
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| Format: | Article |
| Language: | English |
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MDPI AG
2019-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/12/2204 |
| _version_ | 1818289915809497088 |
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| author | José Luis Casals-Sainz Aurora Costales Castro Evelio Francisco Ángel Martín Pendás |
| author_facet | José Luis Casals-Sainz Aurora Costales Castro Evelio Francisco Ángel Martín Pendás |
| author_sort | José Luis Casals-Sainz |
| collection | DOAJ |
| description | Tetrel bonds, the purportedly non-covalent interaction between a molecule that contains an atom of group 14 and an anion or (more generally) an atom or molecule with lone electron pairs, are under intense scrutiny. In this work, we perform an interacting quantum atoms (IQA) analysis of several simple complexes formed between an electrophilic fragment (A) (CH<sub>3</sub>F, CH<sub>4</sub>, CO<sub>2</sub>, CS<sub>2</sub>, SiO<sub>2</sub>, SiH<sub>3</sub>F, SiH<sub>4</sub>, GeH<sub>3</sub>F, GeO<sub>2</sub>, and GeH<sub>4</sub>) and an electron-pair-rich system (B) (NCH, NCO-, OCN-, F-, Br-, CN-, CO, CS, Kr, NC-, NH<sub>3</sub>, OC, OH<sub>2</sub>, SH-, and N<sub>3</sub>-) at the aug-cc-pvtz coupled cluster singles and doubles (CCSD) level of calculation. The binding energy (<inline-formula> <math display="inline"> <semantics> <msubsup> <mi>E</mi> <mi>bind</mi> <mi>AB</mi> </msubsup> </semantics> </math> </inline-formula>) is separated into intrafragment and inter-fragment components, and the latter in turn split into classical and covalent contributions. It is shown that the three terms are important in determining <inline-formula> <math display="inline"> <semantics> <msubsup> <mi>E</mi> <mi>bind</mi> <mi>AB</mi> </msubsup> </semantics> </math> </inline-formula>, with absolute values that increase in passing from electrophilic fragments containing C, Ge, and Si. The degree of covalency between A and B is measured through the real space bond order known as the delocalization index (<inline-formula> <math display="inline"> <semantics> <msup> <mi>δ</mi> <mi>AB</mi> </msup> </semantics> </math> </inline-formula>). Finally, a good linear correlation is found between <inline-formula> <math display="inline"> <semantics> <msup> <mi>δ</mi> <mi>AB</mi> </msup> </semantics> </math> </inline-formula> and <inline-formula> <math display="inline"> <semantics> <msubsup> <mi>E</mi> <mi>xc</mi> <mi>AB</mi> </msubsup> </semantics> </math> </inline-formula>, the exchange correlation (xc) or covalent contribution to <inline-formula> <math display="inline"> <semantics> <msubsup> <mi>E</mi> <mi>bind</mi> <mi>AB</mi> </msubsup> </semantics> </math> </inline-formula>. |
| first_indexed | 2024-12-13T02:19:52Z |
| format | Article |
| id | doaj.art-d15901b5effe423694ecbe2f92acb77f |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-13T02:19:52Z |
| publishDate | 2019-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-d15901b5effe423694ecbe2f92acb77f2022-12-22T00:02:48ZengMDPI AGMolecules1420-30492019-06-012412220410.3390/molecules24122204molecules24122204Tetrel Interactions from an Interacting Quantum Atoms PerspectiveJosé Luis Casals-Sainz0Aurora Costales Castro1Evelio Francisco2Ángel Martín Pendás3Departamento de Química Física y Analítica, Julián Clavería, 6, Facultad de Química, Universidad de Oviedo, 33006 Oviedo, SpainDepartamento de Química Física y Analítica, Julián Clavería, 6, Facultad de Química, Universidad de Oviedo, 33006 Oviedo, SpainDepartamento de Química Física y Analítica, Julián Clavería, 6, Facultad de Química, Universidad de Oviedo, 33006 Oviedo, SpainDepartamento de Química Física y Analítica, Julián Clavería, 6, Facultad de Química, Universidad de Oviedo, 33006 Oviedo, SpainTetrel bonds, the purportedly non-covalent interaction between a molecule that contains an atom of group 14 and an anion or (more generally) an atom or molecule with lone electron pairs, are under intense scrutiny. In this work, we perform an interacting quantum atoms (IQA) analysis of several simple complexes formed between an electrophilic fragment (A) (CH<sub>3</sub>F, CH<sub>4</sub>, CO<sub>2</sub>, CS<sub>2</sub>, SiO<sub>2</sub>, SiH<sub>3</sub>F, SiH<sub>4</sub>, GeH<sub>3</sub>F, GeO<sub>2</sub>, and GeH<sub>4</sub>) and an electron-pair-rich system (B) (NCH, NCO-, OCN-, F-, Br-, CN-, CO, CS, Kr, NC-, NH<sub>3</sub>, OC, OH<sub>2</sub>, SH-, and N<sub>3</sub>-) at the aug-cc-pvtz coupled cluster singles and doubles (CCSD) level of calculation. The binding energy (<inline-formula> <math display="inline"> <semantics> <msubsup> <mi>E</mi> <mi>bind</mi> <mi>AB</mi> </msubsup> </semantics> </math> </inline-formula>) is separated into intrafragment and inter-fragment components, and the latter in turn split into classical and covalent contributions. It is shown that the three terms are important in determining <inline-formula> <math display="inline"> <semantics> <msubsup> <mi>E</mi> <mi>bind</mi> <mi>AB</mi> </msubsup> </semantics> </math> </inline-formula>, with absolute values that increase in passing from electrophilic fragments containing C, Ge, and Si. The degree of covalency between A and B is measured through the real space bond order known as the delocalization index (<inline-formula> <math display="inline"> <semantics> <msup> <mi>δ</mi> <mi>AB</mi> </msup> </semantics> </math> </inline-formula>). Finally, a good linear correlation is found between <inline-formula> <math display="inline"> <semantics> <msup> <mi>δ</mi> <mi>AB</mi> </msup> </semantics> </math> </inline-formula> and <inline-formula> <math display="inline"> <semantics> <msubsup> <mi>E</mi> <mi>xc</mi> <mi>AB</mi> </msubsup> </semantics> </math> </inline-formula>, the exchange correlation (xc) or covalent contribution to <inline-formula> <math display="inline"> <semantics> <msubsup> <mi>E</mi> <mi>bind</mi> <mi>AB</mi> </msubsup> </semantics> </math> </inline-formula>.https://www.mdpi.com/1420-3049/24/12/2204energy partitioninteracting quantum atomsquantum theory of atoms in moleculesdelocalization indexcovalent interactionself-energy |
| spellingShingle | José Luis Casals-Sainz Aurora Costales Castro Evelio Francisco Ángel Martín Pendás Tetrel Interactions from an Interacting Quantum Atoms Perspective Molecules energy partition interacting quantum atoms quantum theory of atoms in molecules delocalization index covalent interaction self-energy |
| title | Tetrel Interactions from an Interacting Quantum Atoms Perspective |
| title_full | Tetrel Interactions from an Interacting Quantum Atoms Perspective |
| title_fullStr | Tetrel Interactions from an Interacting Quantum Atoms Perspective |
| title_full_unstemmed | Tetrel Interactions from an Interacting Quantum Atoms Perspective |
| title_short | Tetrel Interactions from an Interacting Quantum Atoms Perspective |
| title_sort | tetrel interactions from an interacting quantum atoms perspective |
| topic | energy partition interacting quantum atoms quantum theory of atoms in molecules delocalization index covalent interaction self-energy |
| url | https://www.mdpi.com/1420-3049/24/12/2204 |
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