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Structures and Energetics of E 2 H 3 + (E = As, Sb, and Bi) Cations.
- Source :
-
The journal of physical chemistry. A [J Phys Chem A] 2024 Jan 25; Vol. 128 (3), pp. 563-571. Date of Electronic Publication: 2024 Jan 16. - Publication Year :
- 2024
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Abstract
- E <subscript>2</subscript> H <subscript>2</subscript> (E = As, Sb, Bi) structures involving multiple bonds have attracted much attention recently. The E <subscript>2</subscript> H <subscript>3</subscript> <superscript>+</superscript> cations (protonated E <subscript>2</subscript> H <subscript>2</subscript> ) are predicted to be viable with substantial proton affinities (>180 kcal/mol). Herein, the bonding characters and energetics of a number of E <subscript>2</subscript> H <subscript>3</subscript> <superscript>+</superscript> isomers are explored through CCSD(T) and DFT methods. For the As <subscript>2</subscript> H <subscript>3</subscript> <superscript>+</superscript> system, the CCSD(T)/cc-pVQZ-PP method predicts that the vinylidene-like structure lies lowest in energy, with the trans and cis isomers higher by 6.7 and 9.3 kcal/mol, respectively. However, for Sb <subscript>2</subscript> H <subscript>3</subscript> <superscript>+</superscript> and Bi <subscript>2</subscript> H <subscript>3</subscript> <superscript>+</superscript> systems, the trans isomer is the global minimum, while the energies of the cis and vinylidene-like structures are higher, respectively, by 2.0 and 2.4 kcal/mol for Sb <subscript>2</subscript> H <subscript>3</subscript> <superscript>+</superscript> and 1.6 and 15.0 kcal/mol for Bi <subscript>2</subscript> H <subscript>3</subscript> <superscript>+</superscript> . Thus, the vinyledene-like structure is the lowest energy for the arsenic system but only a transition state of the bismuth system. With permanent dipole moments, all minima may be observable in microwave experiments. Besides, we have also obtained transition states and planar-cis structures with higher energies. The current results should provide new insights into the various isomers and provide a number of predictions for future experiments.
Details
- Language :
- English
- ISSN :
- 1520-5215
- Volume :
- 128
- Issue :
- 3
- Database :
- MEDLINE
- Journal :
- The journal of physical chemistry. A
- Publication Type :
- Academic Journal
- Accession number :
- 38227954
- Full Text :
- https://doi.org/10.1021/acs.jpca.3c05945