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1 Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Supplementary information Computational Methodology The def2-tzpp basis set 1 (obtained from the EMSL Basis Set Exchange 2,3 ) was used for all elements except uranium. The def2-tzpp basis set is all electron for F, N, P and As; for Sb, a 28 electron effective core potential (ECP) is used and for Bi a 60 electron ECP. For uranium, the 60-electron quasi-relativistic ECP of the Stuttgart/Cologne Group was used along with the associated atomic natural orbital basis set. 4,5,6 Calculations were performed with Molpro version , 7 using the CASSCF program `Multi, 8,9 and the second-order multiconfigurational perturbation theory program rs2c. 10 Geometry optimisations at the CASSCF level of theory were performed for all molecules NUF3-BiUF3; geometry optimisations at the CASPT2 level of theory were performed for NUF3, PUF3 and AsUF3. Geometry optimisations were first performed in Cs symmetry, but the optimised geometry of NUF3 was approximately C3v, and was re-optimised in that point group. CASPT2 geometry optimisations and harmonic frequency calculations were numerical, due to the lack of analytical gradients in the rs2c program. A level shift of 0.1 was applied for NUF3, and 0.3 for PUF3 and AsUF3 (unless otherwise noted in the SI). Wavefunctions were calculated in Cs symmetry (regardless of the point group of the geometry optimisation) with both space-symmetric and antisymmetric wavefunctions optimised at the singlet, triplet and quintet multiplicities--the effects of spin-orbit coupling were not taken into account. Quantum Theory of Atoms-in-Molecules (QTAIM) 11 analyses were performed with AIMALL, 12 using.wfx files generated by the Molden2AIM program. 13 Calculated states of EUF3 at CASSCF (E = N Bi) and CASPT2 (E = N, P, As) levels of theory. A [6,16] active space is used in all cases. All states are geometrically optimised. Electronic energy relative to the global minimum, electronic energy, natural orbital occupancies, effective bond orders and E-U bond lengths (in ångstrom) given.

2 Electronic States Table S1: NUF3 CASSCF/def2-TZVPP (N, F), SDD (U), optimised geometry Eel / ev Eel / Ha σ π π* σ* f (n.b) BOeff r(n-u) / Å 1A' A" A" A' A' A" Table S2: NUF3 CASPT2/def2-TZVPP (N, F), SDD (U), optimised geometry, level shift = 0.1 Eel / ev Eel / Ha σ π π* σ* f (n.b) BOeff r(n-u) / Å 1A' A"* A' A" A"* A'* *level shift = 0.2 level shift = 0.5 Table S3: PUF3 CASSCF/def2-TZVPP (P, F), SDD (U), optimised geometry Eel / ev Eel / Ha σ π π* σ* f (n.b) BOeff r(p-u) / Å 1A' A" A' A" A" A'

3 Table S4: PUF3 CASPT2/def2-TZVPP (P, F), SDD (U), optimised geometry, level shift = 0.3 Eel / ev Eel / Ha σ π π* σ* f (n.b) BOeff r(p-u) / Å 1A' A" A' A" A' A" Table S5: AsUF3 CASSCF/def2-TZVPP (As, F), SDD (U), optimised geometry Eel / ev Eel / Ha σ π π* σ* f (n.b) BOeff r(as-u) / Å 5A" A' A' A" A' A" Table S6: AsUF3 CASPT2/def2-TZVPP (As, F), SDD (U), optimised geometry, level shift = 0.3 Eel / ev Eel / Ha σ π π* σ* f (n.b) BOeff r(as-u) / Å 1A' A" A' A" A' A"* *level shift = 0.5

4 Table S7: SbUF3 CASSCF/def2-TZVPP (Sb, F), SDD (U), optimised geometry Eel / ev Eel / Ha σ π π* σ* f (n.b) BOeff r(sb-u) / Å 5A" A' A' A' A" A" Table S8: BiUF3 CASSCF/def2-TZVPP (As, F), SDD (U), optimised geometry Eel / ev Eel / Ha σ π π* σ* f (n.b) BOeff r(bi-u) / Å 1A' A" A' A" A" A' Frequency Calculations ([6,16] CASPT2) Table S9: Frequency calculations at the CASPT2 level of theory. Frequency calculations are numerical, and performed without wavefunction symmetry. Frequencies given in cm -1 U-E a1 / a' a1 / a' e / a' e / a" a1 / a' e / a' e / a" E- e / a' E- e / a" #imag. freq. NUF3 1 A i 0.73i 2 PUF3 1 A' i 46.08i 2 AsUF3 1 A' i i 69.44i 3 Optimised Geometries Z matrix variables of the optimised geometries are given in ångstrom for bond lengths and degrees for angles. Z-matrix all of the form: U, E, U, B1, F1, U, B2, E, A1, F2, U, B3, E, A2, F1, D1, 0, F3, U, B3, E, A2, F1, -D1, 0,

5 Table S10: NUF3 CASSCF [6,16] optimised geometries B1 / Å B2 / Å B3 / Å A1 / A2 / D1 / Table S11: NUF3 CASPT2 [6,16] optimised geometries B1 / Å B2 / Å B3 / Å A1 / A2 / D1 / Table S12: PUF3 CASSCF [6,16] optimised geometries B1 / Å B2 / Å B3 / Å A1 / A2 / D1 / Table S13: PUF3 CASPT2 [6,16] optimised geometries B1 / Å B2 / Å B3 / Å A1 / A2 / D1 /

6 Table S14: PUF3 CASPT2 [6,6] optimised geometry 1A' B1 / Å B2 / Å B3 / Å A1 / A2 / D1 / Table S15: AsUF3 CASSCF [6,16] optimised geometries B1 / Å B2 / Å B3 / Å A1 / A2 / D1 / Table S16: AsUF3 CASPT2 [6,16] optimised geometries B1 / Å B2 / Å B3 / Å A1 / A2 / D1 / Table S17: SbUF3 CASSCF [6,16] optimised geometries B1 / Å B2 / Å B3 / Å A1 / A2 / D1 /

7 Table S18: BiUF3 CASSCF [6,16] optimised geometries B1 / Å B2 / Å B3 / Å A1 / A2 / D1 / Table S19: PUF3 SA-CASSCF [6,16] pseudo-natural orbital occupancies for each state, electronic energies and relative energies. All states 1 A' symmetry, performed at the CASPT2 optimised geometry. A' A" State σ π π* 5fU 5fU 5fU 3dP 3dP 3dP 3dP π f π* 5fU 3dP 3dP 5fU + π* Eel / Ha E / ev References 1 F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys., 2005, 7, D. Feller, J. Comput. Chem., 1996, 17, K. L. Schuchardt, B. T. Didier, T. Elsethagen, L. Sun, V. Gurumoorthi, J. Chase, J. Li and T. L. Windus, J. Chem. Inf. Model., 2007, 47, X. Cao, M. Dolg and H. Stoll, J. Chem. Phys., 2003, 118, X. Cao and M. Dolg, THEOCHEM, 2004, 673, W. Küchle, M. Dolg, H. Stoll and H. Preuss, J. Chem. Phys., 1994, 100, H.-J. Werner, P. J. Knowles, G. Knizia, F. R. Manby, M. Schütz et al., MOLPRO, version , P. J. Knowles and H. J. Werner, Chem. Phys. Letters, 1985, 115, H. J. Werner and P. J. Knowles, J. Chem. Phys., 1985, 82, P. Celani and H. J. Werner, J. Chem. Phys., 2000, 112, R. F. Bader, Atoms in molecules: a quantum theory, Clarendon Pr., O. P. K. U. Todd A. Keith, TK Gristmill Software, AIMAll (Version ), W. Zou, D. Nori-Shargh and J. E. Boggs, J. Phys. Chem. A, 2013, 117,