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. 2024 Jan 25;128(3):563-571.
doi: 10.1021/acs.jpca.3c05945. Epub 2024 Jan 16.

Structures and Energetics of E2H3+ (E = As, Sb, and Bi) Cations

Shu-Hua Xia  1 , Jihuan He  1 , Zhuoqun Liu  1 , Yunhan Liu  1 , Yan Zhang  1 , Yaoming Xie  2 , Mitchell E Lahm  2 , Gregory H Robinson  2 , Henry F Schaefer 3rd  2
Affiliations

Structures and Energetics of E2H3+ (E = As, Sb, and Bi) Cations

Shu-Hua Xia et al. J Phys Chem A. .

Abstract

E2H2 (E = As, Sb, Bi) structures involving multiple bonds have attracted much attention recently. The E2H3+ cations (protonated E2H2) are predicted to be viable with substantial proton affinities (>180 kcal/mol). Herein, the bonding characters and energetics of a number of E2H3+ isomers are explored through CCSD(T) and DFT methods. For the As2H3+ 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 Sb2H3+ and Bi2H3+ 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 Sb2H3+ and 1.6 and 15.0 kcal/mol for Bi2H3+. 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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Geometries and energetics for three As2H3+ equilibrium geometries. Bond distances are in Å and relative energies (bold face) in kcal/mol.
Figure 2
Figure 2
Geometries and energetics for four As2H3+ transition states. Bond distances are in Å and relative energies (bold face) to the vinylidene-like global minimum (in Figure 1) in kcal/mol. The imaginary vibrational frequencies (in cm–1) are shown in parentheses.
Figure 3
Figure 3
Geometries and energetics for three Sb2H3+ equilibrium geometries. Bond distances are in Å and energies (bold face) in kcal/mol.
Figure 4
Figure 4
Geometries and energetics for five Sb2H3+ transition states. Bond distances are in Å and energies (bold face) relative to the trans global minimum (in Figure 3) in kcal/mol. The imaginary vibrational frequencies (in cm–1) are shown in parentheses.
Figure 5
Figure 5
Geometries and energetics for two Bi2H3+ equilibrium geometries. Bond distances are in Å and energies (bold face) in kcal/mol.
Figure 6
Figure 6
Geometries and energetics for four Bi2H3+ transition states. Bond distances are in Å and energies (bold face) relative to the trans global minimum (in Figure 5) in kcal/mol. The imaginary vibrational frequencies (in cm–1) are shown in parentheses.
Figure 7
Figure 7
HOMO orbitals of the vinylidene-like structures of the As2H3+, Sb2H3+, and Bi2H3+ systems.
See this image and copyright information in PMC

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