Supporting Information. Oxidation States, Geometries, and Electronic Structures of

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1 1 Supporting Information Oxidation States, Geometries, and Electronic Structures of Plutonium Tetroxide PuO 4 : Is Octavalent Pu Viable? Wei HUANG, Wen-Hua XU, Jing SU, W.H.E. SCHWARZ and Jun LI Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing , China CONTENTS 1. Software references S1 to S4 p Table S1. Various isomeric states of PuO 4. p Table S2. 5 C 2v -PuO 4. Vertical electronic excitations from CASSCF/CASPT2/SO calculations. p. 4/5

2 2 SOFTWARE REFERENCES S1 - Gaussian 09, Revision C.01: M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox. Gaussian, Wallingford CT, S2 ADF 2010, E.J. Baerends, T. Ziegler, J. Autschbach, D. Bashford, A. Bérces, F.M. Bickelhaupt, C. Bo, P.M. Boerrigter, L. Cavallo, D.P. Chong, L. Deng, R.M. Dickson, D.E. Ellis, M. van Faassen, L. Fan, T.H. Fischer, C. Fonseca Guerra, A. Ghysels, A. Giammona, S.J.A. van Gisbergen, A.W. Götz, J.A. Groeneveld, O.V. Gritsenko, M. Grüning, S. Gusarov, F.E. Harris, P. van den Hoek, C.R. Jacob, H. Jacobsen, L. Jensen, J.W. Kaminski, G. van Kessel, F. Kootstra, A. Kovalenko, M.V. Krykunov, E. van Lenthe, D.A. McCormack, A. Michalak, M. Mitoraj, J. Neugebauer, V.P. Nicu, L. Noodleman, V.P. Osinga, S. Patchkovskii, P.H.T. Philipsen, D. Post, C.C. Pye, W. Ravenek, J.I. Rodríguez, P. Ros, P.R.T. Schipper, G. Schreckenbach, J.S. Seldenthuis, M. Seth, J.G. Snijders, M. Solà, M. Swart, D. Swerhone, G. te Velde, P. Vernooijs, L. Versluis, L. Visscher, O. Visser, F. Wang, T.A. Wesolowski, E.M. van Wezenbeek, G. Wiesenekker, S.K. Wolff, T.K. Woo, A.L. Yakovlev. SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, S3 - MOLPRO, version , a package of ab initio programs, H.-J.Werner, P. J. Knowles, R. Lindh, F. R. Manby, M. Schütz, P. Celani, T. Korona, A. Mitrushenkov, G. Rauhut, T. B. Adler, R. D. Amos, A. Bernhardsson, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, E. Goll, C. Hampel, G. Hetzer, T. Hrenar, G. Knizia, C. K oppl, Y. Liu, A. W. Lloyd, R. A. Mata, A. J. May, S. J. McNicholas, W. Meyer, M. E. Mura, A. Nicklass, P. Palmieri, K. Pfl uger, R. Pitzer, M. Reiher, U. Schumann, H. Stoll, A. J. Stone, R. Tarroni, T. Thorsteinsson, M.Wang, and A. Wolf,, see S4 - NBO 5.G, E. D. Glendening, J. K. Badenhoop, A. E. Reed, J. E. Carpenter, J. A. Bohmann, C. M. Morales, and F. Weinhold. Theoretical Chemistry Institute, University of Wisconsin, Madison WI, 2004.

3 3 Table S1. CCSD(T) and CASPT2 results of various isomeric states of PuO 4. Sym 1) E HL 2) CCSD(T) 3) CASPT2 4) E T 1 D 1 AS C 0 C 1 5 C 2v (12,12) 89% 1% 1 D 4h (12,13) 67% 1% 3 C 2v 5) (12,11) 93% 1% 5 D 2h (10,10) 90% 1% 5 D 2d (12,11) 93% 2% 1 T d ) (24,19) 38% 2% 1) Sym = Spin-Space symmetry; 2) E HL = HOMO-LUMO energy gap (in ev); 3) CCSD(T) calculations: E = energy above the 5 C 2v (PuO 2 )O 2 ground state (in kj/mol), T 1 and D 1 diagnostics 1-3 ; 4) CASPT2 calculations: AS = active space, C 0 and C 1 = weights of the two most important configurations; 5) planar isomer; 6) CCD approximation. References: (1) Lee T. J.; Taylor, P. R. Int. J. Quant. Chem. 1989, S23, 199. (2) Janssen, C. L.; Nielsen, I. M. B. Chem. Phys. Lett. 1998, 290, 423. (3) Lee, T. J. Chem. Phys. Lett. 2003, 372, 362.

4 4 Table S2. 5 C 2v -PuO 4. Vertical electronic excitation properties from CASSCF/CASPT2/SO calculations. No. 1) ΔE (cm -1 ) 2) Leading term(s) 3) 10 6 f (au) 4) 1 (GS) Far and Near IR A B B 1 5 A A B A A 2 3 A B B B Vis region

5 Etc. VUV region A A 2 1 B A A A A A A B ) No. = State number beginning with 1 for the ground state; 2) ΔE = vertical excitation energy above the spin-orbit ground state; 3) leading configuration term functions; 4) f = electric dipole oscillator strength.