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Theoretical Analysis of an Anion-π Complex: I‒‧C6F6
徐昕
Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Key Laboratory of Computational Physical Sciences, Department of Chemistry, Fudan University, Shanghai 200433, People’s Republic of China.
Abstract:
Recently, Anst?ter and co-workers (Anst?ter, et al. J. Am. Chem. Soc. 141, 6132 (2019)) have provided the first photoelectron spectroscopic determination of the anion?π bond strength (De) using iodide-hexafluorobenzene (I??C6F6) as the archetypical system. In combination with an equation-of-motion coupled cluster theory, namely EOM-IP-CCSD(dT), using Dunning’s aug-cc-pVDZ (aVDZ) basis set, De in I??C6F6 was found to be ?0.53 eV with an uncertainty less than ±0.03 eV. The interaction was claimed to arise for a large part from correlation forces (41%) with only a 23% contribution from electrostatic forces. In the present work, we performed the coupled-cluster with single and double and perturbative triple excitations, CCSD(T), calculations. We found that CCSD(T)/aVDZ can have an uncertainty up to 0.113 eV due to the basis set incompleteness. Our calculations disclosed that the previous calculations on the electrostatic contribution is concealed by the contributions from the exchange and Pauli repulsion. The electrostatic contribution is actually determinant, being more than double of the correlation contribution in the I??C6F6 complex at the equilibrium binding distance.
Key words:  Anion- interactions, electrostatic interaction, correlation, OEE, XYG3, CCSD(T)
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Theoretical Analysis of an Anion-π Complex: I‒‧C6F6
徐昕
Xiamen University
摘要:
Recently, Anst?ter and co-workers (Anst?ter, et al. J. Am. Chem. Soc. 141, 6132 (2019)) have provided the first photoelectron spectroscopic determination of the anion?π bond strength (De) using iodide-hexafluorobenzene (I??C6F6) as the archetypical system. In combination with an equation-of-motion coupled cluster theory, namely EOM-IP-CCSD(dT), using Dunning’s aug-cc-pVDZ (aVDZ) basis set, De in I??C6F6 was found to be ?0.53 eV with an uncertainty less than ±0.03 eV. The interaction was claimed to arise for a large part from correlation forces (41%) with only a 23% contribution from electrostatic forces. In the present work, we performed the coupled-cluster with single and double and perturbative triple excitations, CCSD(T), calculations. We found that CCSD(T)/aVDZ can have an uncertainty up to 0.113 eV due to the basis set incompleteness. Our calculations disclosed that the previous calculations on the electrostatic contribution is concealed by the contributions from the exchange and Pauli repulsion. The electrostatic contribution is actually determinant, being more than double of the correlation contribution in the I??C6F6 complex at the equilibrium binding distance.
关键词:  Anion- interactions, electrostatic interaction, correlation, OEE, XYG3, CCSD(T)
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