On the Covalent Character of Rare Gas Bonding Interactions: a New Kind of Weak Interaction” by Wenli Zou, Davood Nori-Shargh, and James E

Supporting Information to the article entitled

“On the covalent character of rare gas bonding interactions: a new kind of weak interaction” by Wenli Zou, Davood Nori-Shargh, and James E. Boggs

Table S1. Equilibrium geometries (bond length in Å and bond angle in degree) of some rare gas containing systems. All of them have C ∞v symmetry except HeB(CH) 3 with C 3v .

No. Mol. State Structure parameters Ref. 1 FHeO - 1Σ+ He-O=1.100, He-F=1.621 61 2 HHeF 1Σ+ He-H=0.818, He-F=1.418 63 3 HArF 1Σ+ Ar-H=1.329, Ar-F=1.967 6 4 HeCuF 1Σ+ He-Cu=1.659, Cu-F=1.732 26 5 HeAgF 1Σ+ He-Ag=2.143, Ag-F=1.967 26 6 HeAuF 1Σ+ He-Au=1.841, Au-F=1.904 26 7 NeCuF 1Σ+ Ne-Cu=2.172, Cu-F=1.738 26 8 NeAgF 1Σ+ Ne-Ag=2.700, Ag-F=1.974 26 9 NeAuF 1Σ+ Ne-Au=2.444, Au-F=1.917 26 10 ArCuF a) 1Σ+ Ar-Cu=2.219, Cu-F=1.753 12 11 ArAgF a) 1Σ+ Ar-Ag=2.558, Ag-F=1.986 13 12 ArAuF a) 1Σ+ Ar-Au=2.391, Au-F=1.918 14 13 KrCuF a) 1Σ+ Kr-Cu=2.316, Cu-F=1.745 11 14 KrAgF a) 1Σ+ Kr-Ag=2.594, Ag-F=1.984 b) 10 15 KrAuF a) 1Σ+ Kr-Au=2.460, Au-F=1.918 10 16 XeCuF a) 1Σ+ Xe-Cu=2.430, Cu-F=1.745 9 17 XeAgF a) 1Σ+ Xe-Ag=2.666, Ag-F=1.983 8 18 XeAuF a) 1Σ+ Xe-Au=2.543, Au-F=1.918 7 19.a HePtF 2Σ+ He-Pt=1.828, Pt-F=1.881 31 19.b 2Π He-Pt=1.860, Pt-F=1.862 19.c 2∆ He-Pt=1.798, Pt-F=1.900 20 HePtXe 1Σ+ He-Pt=1.818, Xe-Pt=2.509 33 1 21 HeB(CH) 3 A1 He-B=1.355, B-C=1.493, C-H=1.066, 32 C-B-He=143.7, H-C-B=161.4 22 HeBeO 1Σ+ He-Be=1.522, Be-O=1.330 25 23 NeBeO 1Σ+ Ne-Be=1.798, Be-O=1.339 37 24 ArBeO 1Σ+ Ar-Be=2.076, Be-O=1.341 37 25 KrBeO 1Σ+ Kr-Be=2.211, Be-O=1.343 37 26 XeBeO 1Σ+ Xe-Be=2.385, Be-O=1.344 37 a) Experimental geometries. b) R 0 is used here. 1.957 Å in ref 10 may be a typo.

Natural charge and WBI. It has been reported that natural charge and WBI may have problems in the case of some metal compounds. S1-S4 For example, the WBI value of the Be-O bond is only 0.6, being much smaller than the Mayer bond order (MBO) of 1.8 and the empirical bond order of 2.0. This problem also exists in MgO, CaO, ZnO, and so on. For rare gas bonds, however, NBO analysis provides reasonable results, and the WBI values are qualitatively in line with the MBO ones. So NBO

S1 analysis can be used safely in this research.

References

(S1) Maseras, F.; Morokuma, K. Chem. Phys. Lett. 1992 , 195, 500-504.

(S2) Clark, A. E.; Sonnenberg, J. L.; Hay, P. J.; Martin, R. L. J. Chem. Phys. 2004 , 121, 2563-2570.

(S3) Landis, C. R.; Weinhold, F. J. Comput. Chem. 2007 , 28, 198-203.

(S4) Lu, T.; Chen, F.-W. Acta Phys.-Chim. Sin. 2012 , 28, 1-18.

S2 Programs used in this research

Molden2AIM It converts the data format from Molden to AIM's WFN. The latter format can be used in AIMPAC, AIM2000, AIMALL, PAMoC, TopMoD, Xaim, MORPHY98, Multiwfn, ProMolDen, and so on.

Molden file can be generated using the following quantum chemistry softwares, but some of them do not work with Molden2AIM. 1. MOLPRO 2. MOLCAS (spherical basis functions only) 3. deMon2k 4. Q-Chem (spherical S, P, D, and F or Cartesian S, P, and D basis functions) 5. CFour (S, P, D, and F basis functions; insert a command line [Program] Cfour into the Molden file) 6. Turbomole (insert a command line [Program] Turbomole into the Molden file) 7. ORCA (insert a command line [Program] Orca into the Molden file) 8. Columbus (thanks to Dr. Marat Talipov for testing) 9. Priroda (thanks to Dr. Evgeniy Pankratyev for testing) 10.StoBe (not tested) 11.TeraChem (not tested) 12.ACES II and III (not supported) 13.DALTON (not supported) 14.Jaguar (not supported)

Limitations: 1. In general, only S, P, D, F, and G Gaussian basis functions are supported by Molden2AIM. AIMALL can also use H functions, but the Molden format cannot. 2. ECP or MCP is not supported because there is no ECP data block in the Molden format. See AIMALL for the analysis using ECP. 3. The total energy and virial ratio printed on the last line of the WFN file do not make sense. If they are used in your AIM analysis, please modify them manually.

NBO2Molden It saves NBO's plot files (*.31 ~ *.40) into Molden format, which can be plotted using Molden, GabEdit, MacMolPlt, and so on.

MolBO It reads basis sets, overlap matrix, Fork matrix, density matrix, ... from MOLPRO's output file (use GPRINT and MATROP commands to obtain these data; see the examples), and prepares NBO's *.47 file. It also calculates Mayer bond orders (MBO).

Electronic density can be computed using the following theoretical methods:

S3 1. SCF: RHF, ROHF, UHF, RDFT, RODFT, UDFT 2. Density Fitting (nosym): DF-HF, DF-KS 3. Post-HF: MP2, MP3, CCSD, QCISD, QCISD(T), EOM-CCSD, Full-CI 4. Local Post-HF (nosym): LMP2 5. MC/MR: MCSCF, CASVB, MRCI (including SRCI), CASPT2 (including SRMP2)

Supports: 1. MOLPRO 2006 - 2010. Lower MOLPRO versions were not tested. 2. NBO 3.0 and 5.x. Version 4.x has not been tested, but there should be no problem.

Limitations: 1. Symmetry equivalent atoms are not allowed. It is necessary to decrease the symmetry until all the atoms are symmetry unique. For example, use C 2v instead of D 2h for CO 2, C s instead of C 2v for H 2O, and C 1 instead of C s for CF 4. 2. For the all-electron relativistic calculations (DKHn), do not print kinetic energy and potential energy matrices because they are non-relativistic. Please read the manual for other questions.