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Zhang-yun Liu, Zheng Chen, Xin Xu. Theoretical Analysis of an Anion-π Complex: I-dC6F6[J]. Chinese Journal of Chemical Physics , 2020, 33(3): 285-290. doi: 10.1063/1674-0068/cjcp2005069
 Citation: Zhang-yun Liu, Zheng Chen, Xin Xu. Theoretical Analysis of an Anion-π Complex: I-dC6F6[J]. Chinese Journal of Chemical Physics , 2020, 33(3): 285-290.

# Theoretical Analysis of an Anion-π Complex: I-dC6F6

##### doi: 10.1063/1674-0068/cjcp2005069
• Corresponding author: Xin Xu.xxchem@fudan.edu.cn
• Accepted Date: 2020-05-19
• Publish Date: 2020-06-27
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Phys. 131, 014102 (2009). [24] H. J. Werner, P. J. Knowles, G. Knizia, F. R. Manby, and M. Schütz, WIREs Comput. Mol. Sci. 2, 242 (2012). doi:  10.1002/wcms.82 [25] M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, and J. A. Montgomery, J. Comput. Chem. 14, 1347 (1993). [26] E. C. Lee, D. Kim, P. Jurecka, P. Tarakeshwar, P. Hobza, and K. S. Kim, J. Phys. Chem. A 111, 3446 (2007). [27] T. C. Dinadayalane and J. Leszczynski, Struct. Chem. 20, 11 (2009). [28] A. D. Becke, Phys. Rev. A 38, 3098 (1988). [29] C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988). [30] P. J. Stephens, F. J. Devlin, C. F. Chabalowski, and M. J. Frisch, J. Phys. Chem. 98, 11623 (1994). [31] J. P. Perdew and K. Schmidt, AIP Conf. Proc. 577, 1 (2001). [32] A. Görling and M. Levy, Phys. Rev. B 47, 13105 (1993). [33] I. Y. Zhang and X. Xu, A New-Generation Density Functional: Towards Chemical Accuracy for Chemistry of Main Group Elements, Heidelberg Springer: Springer Briefs in Molecular Science, (2014). https://www.researchgate.net/publication/258885638_A_New-Generation_Density_Functional_-_Towards_Chemical_Accuracy_for_Chemistry_of_Main_Group_Elements [34] I. Y. Zhang and X. Xu, Int. Rev. Phys. Chem. 30, 115 (2011). [35] N. Q. Su and X. Xu, Annu. Rev. Phys. Chem. 68, 155 (2017). [36] N. Q. Su and X. Xu, WIRES, Comput. Mol. Sci. 6, 721 (2016). [37] I. Y. Zhang, Y. Luo, and X. Xu, J. Chem. Phys. 133, 104105 (2010). [38] C. D. Sherrill, T. Takatani, and E. G. Hohenstein, J. Phys. Chem. A 113, 10146 (2009). [39] á. Vázquez-Mayagoitia, C. D. Sherrill, E. Aprà, and B. G. Sumpter, J. Chem. Theory Comput. 6, 727 (2010). [40] C. D. Sherrill, B. G. Sumpter, M. O. Sinnokrot, M. S. Marshall, E. G. Hohenstein, R. C. Walker, and I. R. Gould, J. Comput. 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###### 通讯作者: 陈斌, bchen63@163.com
• 1.

沈阳化工大学材料科学与工程学院 沈阳 110142

Figures(1)  / Tables(2)

## Theoretical Analysis of an Anion-π Complex: I-dC6F6

##### doi: 10.1063/1674-0068/cjcp2005069
###### Corresponding author:Xin Xu.xxchem@fudan.edu.cn
Zhang-yun Liu, Zheng Chen, Xin Xu. Theoretical Analysis of an Anion-π Complex: I-dC6F6[J]. Chinese Journal of Chemical Physics , 2020, 33(3): 285-290. doi: 10.1063/1674-0068/cjcp2005069
 Citation: Zhang-yun Liu, Zheng Chen, Xin Xu. Theoretical Analysis of an Anion-π Complex: I-dC6F6[J]. Chinese Journal of Chemical Physics , 2020, 33(3): 285-290.
• Anion-π interaction refers to an attractive force between an anion and an electron-deficient π system [1-3]. Although it is now widely recognized as an important nonbonded interaction in supramolecular and biological chemistry [4-7], there is few direct spectroscopic determination of its intrinsic bonding strength, while its binding nature is still elusive [8-12].

Recently, Anstöter and co-workers have filled this void to provide a photoelectron spectroscopic determination of the binding strength for the iodide-hexafluorobenzene (I-·C6F6) complex [13]. In combination with high-level electronic structure calculations, the anion-π bond strength (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 electrostatic interaction (23%) and polarization (28%) making up most of the remainder. In their experiment, I- was condensed onto C6F6 using a molecular beam source. The I-·C6F6 complexes were formed by the supersonic expansion, mass-selected by time-of-flight, and intersected with light. The resultant photoelectrons were then analyzed. Theoretically, they have calculated the I-·C6F6 complex with an equation-of-motion coupled cluster theory, namely EOM-IP-CCSD(dT) [14], using the aug-cc-pVDZ (aVDZ for short) basis set [15, 16] at the frozen-core approximation. A rigid potential energy scan was performed by changing the distance (R) between I- and the center of the C6F6 ring. To explore the binding nature, an energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMO [17]) was carried out on the self-consistent field (SCF) energy of the complex plus the correlation contribution. The QChem 5.0 computational package [18] was employed. Quantitatively, the aVDZ basis set used in their work was usually too small to be close to the basis set completeness, although it was a choice limited by the system size. Conceptually, it is generally accepted [8-10] that an anion-π interaction is principally due to the electrostatic forces including the ion-induced polarization, while the correlation forces are usually put in a respectively minor position in the anion-π interactions.

In the present work, we performed the CCSD(T) (i.e. coupled-cluster with single and double and perturbative triple excitations) calculations on the potential energy curve of the I-·C6F6 complex. The same aVDZ basis set [15] was employed for C and F atoms but without invoking the frozen-core approximation. The same effective core potential and the respective basis set (aug-cc-pVDZ-pp [16]) were applied to I-. We have used the Boys-Bernardi counterpoise technique [19] to explore the basis set superposition error (BSSE). We have also performed the CCSD(T)-F12 [20]/aVDZ calculations to further assess the basis set incompleteness. In an attempt to find an accurate and efficient alternative to the expensive CCSD(T) method, we have benchmarked the performances of XYG3 [21] and the long-range-corrected (lrc) XYG3 [22], two doubly hybrid (DH) functionals developed in our groups, using the same aVDZ basis set. To explore the binding nature, we have applied the local molecular orbital energy decomposition analysis (LMO-EDA [23]) method to the CCSD(T) and XYG3 binding energies. The F12 [20] calculations were performed by using the Molpro package [24], the LMO-EDA calculations were performed by using the GAMESS US package [25], and all other calculations were carried out by using a local development-version of QChem 5.0 computational package [18]. We found that CCSD(T)/aVDZ can have an uncertainty up to 0.113 eV due to the basis set incompleteness. We found that the electrostatic contribution is over 128% in the I-·C6F6 complex, which is counterbalanced by the Pauli repulsion. The electrostatic contribution alone clearly outweighs the correlation contribution, although the latter is also important, making a 53% contribution at the equilibrium binding distance (Re).

Our calculation results are presented in Tables Ⅰ and Ⅱ and FIG. 1. Table Ⅰ summarizes the results for the potential energy curve scan of the I-·C6F6 complex, where the C-C and the C-F bond lengths in C6F6 were fixed at 1.3948 Å and 1.3394 Å, respectively. The BSSE effects are indeed strong for the correlated methods. The CCSD(T)/aVDZ method predicts a binding energy of -0.565 eV, which is reduced to -0.452 eV after the full portion of the Boys-Bernardi counterpoise correction [19]. The equilibrium distance is found at Re = 3.52 Å at the level of CCSD(T)/aVDZ, which is extended to 3.70 Å after the BSSE correction. The well of the potential energy curve is rather flat, where the energy difference from the distance R = 3.50 Å to 3.60 Å is only 0.003 eV (Table Ⅰ) at the level of CCSD(T)/aVDZ.

Figure 1.  Energy decomposition analysis [22] applied to the I-·C6F6 complex at the level of CCSD(T). Code: electrostatic contribution (OEE [42]), correlation contribution (COR), polarization contribution (POL), exchange-repulsion (EX-REP = EX+REP [41]), the frozen density term (FRZ = OEE+EX-REP [18]). Note that the electrostatic interaction (OEE) is always attractive, which clearly outweighs in magnitude the contribution from the correlation interaction (COR)

The CCSD(T)-F12/aVDZ method may provide a better way to account for the basis set incompleteness than the Boys-Bernardi counterpoise correction. Table Ⅰ summarizes the results from F12a and F12b. We may infer that F12a yields better results than F12b at the aVDZ basis set [24, 25]. As seen from Table Ⅰ, F12a predicts De = -0.531 eV at Re = 3.54 Å. These compare very well with the fitting data of De = -0.53 eV at Re = 3.56 Å by Anstöter and co-workers [13]. The F12b results are also satisfactory, which yields De = -0.519 eV at Re = 3.55 Å.

It is well known that the Boys-Bernardi counterpoise technique will overcorrect the BSSE, as the monomer cannot take full advantage of the basis sets of the ghost atoms when they are actually occupied by electrons [26, 27]. Kim and co-workers have suggested to use 50% BSSE correction for smaller basis sets [26]. Table Ⅰ also gives the CCSD(T)/aVDZ results with 50% BSSE correction. If it is about to mimic the CCSD(T)-F12a/aVDZ results, a 25% BSSE correction is recommended.

In the wavefunction theory, the Hartree-Fock (HF) theory, by definition, contains no correlation contribution. Still the bond strength is predicted to be -0.326 eV by HF, indicating the importance of electrostatic and polarization interactions. The equilibrium distance is found to be 3.90 Å at the level of HF/aVDZ. BSSE is not significant when the method does not take the excitations into the virtual orbitals into account. After a full portion of BSSE correction, De is reduced to -0.313 eV for HF/aVDZ. Hence, BSSE with HF/aVDZ is about one tenth of that with CCSD(T)/aVDZ.

Table Ⅰ also summarizes the results from B3LYP [28-30]/aVDZ, which leads to De = -0.341 eV at Re = 3.80 Å. The B3LYP results are found to be quite similar to those of HF, although the former shows a slightly stronger binding tendency than the latter. The BSSE effect for B3LYP/aVDZ shall be very similar to that for HF/aVDZ. The close similarity between B3LYP and HF indicates that B3LYP is insufficient to catch up with the correlation effects in the I-·C6F6 complex with the LYP [29] correlation functional.

XYG3 [21] and lrc-XYG3 [22] belong to the fifth rung functional of the Jocob's ladder [31], which not only hybridizes the local exchange (e.g., B88 [28]) with the HF-like exchange as it does in B3LYP, but also hybridizes the local correlation (e.g., LYP [29]) with the second-order perturbation theory (PT2 [32]). The XYG3 type of doubly hybrid (xDH) functionals have been shown to be remarkably accurate in describing the non-covalent interactions of the main group elements [21, 22, 33-36]. The generally good performance of xDH comes naturally from the right physics of the truly nonlocal correlation in the PT2 term.

For the I-·C6F6 complex, the XYG3 method predicts the equilibrium distance for Re = 3.54 Å with the binding energy being De = -0.509 eV. These results are very much similar to the CCSD(T)/aVDZ results with 50% BSSE correction (see Table Ⅰ). Our results highlight the usefulness of XYG3 as a cost-effective substitute of the expensive CCSD(T) for complex real-world systems, indicating the superiority of the xDH functionals to the popular B3LYP functional in describing the correlation effects for the anion-π interactions. On the other hand, it is known that XYG3 does not recover 100% PT2 term at the long range for correlation/dispersion. Hence, it may still fall short of some correlation/dispersion interactions. The lrc-XYG3 method [22] amends XYG3 by adding a distance-dependent PT2 correlation, which leads to De = -0.555 eV at Re = 3.53 Å. The BSSE effect is generally smaller [37], as the PT2 term is scaled by 0.3211. Hence, no BSSE corrections have been applied to all our DFT calculations as commonly done in the literature [21, 22, 38-40], which further simplifies the calculations when applied to complex systems.

As for the binding nature is concerned, the most popular point of view so far is that the anion-π binding interaction is governed by the electrostatic contributions and the ion-induced polarizations together [8-12]. The electrostatic force requires the π system to possess a positive quadrupole moment, thus demanding the π ring to be substituted with electron-withdrawing substituents [1-12]. The results of Anstöter and co-workers [13], however, challenge this popular view that the electrostatic force is determinant in the anion-π interaction. They decomposed the interaction energy in the I-·C6F6 complex at 3.70 Å and claimed that the relative ratio of electrostatic:polarization:correlation is 23:28:41. Hence, while the electrostatic force was found to be an important driver for the anion-π interaction in the I-·C6F6 complex, they concluded that it was the correlation energy that was the dominant contributor [13].

We performed the energy decomposition on the CCSD(T) binding energies using the LMO-EDA approach [23]. The analysis was applied to the HF energy, while the correlation/dispersion energy is obtained from the energy difference between CCSD(T) and HF. The results are summarized in Table Ⅱ, where, in addition to the correlation contribution (COR), and the polarization contribution (POL), there are also electrostatic contribution (OEE), exchange (EX) and Pauli repulsion (REP). The sum of the exchange and Pauli repulsion terms is generally recognized as the exchange-repulsion (EX-REP) term [41], as it represents a quantum effect due to the properly antisymmetrized many-electron wavefunction of the complex constructed from the unrelaxed nonorthogonal occupied orbitals of the monomers. The electrostatic term is also well-defined, which refers to the Coulomb interaction between two unrelaxed monomer electron density distributions on orbitals. As the electron clouds in an anion are always diffusive, it is important to emphasize its orbital nature in describing electrostatic interactions involving anions. To emphasize its difference from other widely used models [8-12], Qzz (ESP), and quadrupole moment (Qzz) where anions are simplified as point charges, we have recently named this electrostatic term as the orbital electrostatic energy (OEE) [42] and found it sheds new light on some typical behaviors of ion-π interactions [43]. Here we emphasize that, in the original ALMO-EDA scheme [17, 18], the sum of OEE and EX-REP is referred as the frozen density term (FRZ), corresponding to bringing infinitely separated monomers into the complex geometry without any relaxation of the monomer orbitals.

As shown in Table Ⅱ for CCSD(T)/aVDZ at R = 3.70 Å, we found that the relative ratio of FRZ:POL:COR is 22:34:44, which is very close in numbers to the ratio of electrostatic:polarization:correlation of 23:28:41 claimed by Anstöter and co-workers [13], with an important qualitative difference that the electrostatic term is replaced by the frozen density term. FIG. 1 depicts the decomposition results along the potential curve. The electrostatic contribution between an anion (e.g. I-) and a positive quadrupole moment (e.g., Qzz = +9.50 B for C6F6 [13]) is always attractive and has to increase in magnitude as the interacting distance decreases. On the other hand, we have the Pauli repulsion, which represents an increasing wall effect upon the decreasing interacting distance. Hence the electrostatic interaction along with other attractive forces is counterbalanced by the Pauli repulsion. As clearly seen from FIG. 1, the OEE term is dominant. For CCSD(T)/aVDZ at R = 3.70 Å, we calculated the relative ratio of OEE:POL:COR to be 102:34:44. At Re = 3.52 Å, the relative ratio of OEE:POL:COR is 128:39:53, while the FRZ ratio is reduced to 8%. Hence, our calculations disclosed that the previous calculations [13] on the electrostatic contribution are concealed by the contributions from the exchange and Pauli repulsion. The correlation effect is important, whereas the electrostatic contribution is actually determinant, being more than double of the correlation contribution in the I-·C6F6 complex at the equilibrium binding distance.

We also extended the LMO-EDA approach [23] to the xDH functionals, decomposing the B3LYP energy while augmented by the additional exchange-correlation contributions from XYG3. The results are also summarized in Table Ⅱ. For XYG3/aVDZ at Re = 3.54 Å, the relative ratio of OEE:POL:COR is found to be 144:47:61. Hence, the XYG3 results are in good accordance with the CCSD(T) results.

In summary, we have performed the CCSD(T)/aVDZ calculations on the potential energy curve of the I-·C6F6 complex. The basis set incompleteness has been assessed using the Boys-Bernardi counterpoise techniques and the F12 techniques. We found that CCSD(T)/aVDZ can have an uncertainty up to 0.113 eV due to the basis set incompleteness, and the results from 25% BSSE corrections or F12a agree well with the fitting data from the literature. We have benchmarked the performances of the xDH functionals of XYG3 and lrc-XYG3. Their results are found to be generally satisfactory within the uncertainty. As the xDH functionals formally scale as O(N5), where \begin{document$N$\end{document is proportional to the system size, they show promise as an economic substitute of the expensive CCSD(T) with an O(\begin{document$N^7$\end{document) scaling. We have applied the LMO-EDA method to the CCSD(T) and the XYG3 binding energies, and reaffirmed the importance of the electrostatic forces in the anion-π interactions.

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