Validation of density functional modeling protocols on experimental bis(mu-oxo)/mu-eta2:eta2-peroxo dicopper equilibria.
The bis(mu-oxo)/mu-eta(2):eta(2)-peroxo equilibria for seven supported Cu(2)O(2) cores were studied with different hybrid and nonhybrid density functional theory models, namely, BLYP, mPWPW, TPSS, TPSSh, B3LYP, mPW1PW, and MPW1K. Supporting ligands 3,3'-iminobis(N,N-dimethylpropylamine), N,N,N',N',N''-pentamethyldipropylenetriamine, N-[2-(pyridin-2-yl)ethyl]-N,N,N'-trimethylpropane-1,3-diamine, bis[2-(2-pyridin-2-yl)ethyl]methylamine, bis[2-(4-methoxy-2-pyridin-2-yl)ethyl]methylamine, bis[2-(4-N,N-dimethylamino-2-pyridin-2-yl)ethyl]methylamine, and 1,4,7-triisopropyl-1,4,7-triazacyclononane were chosen on the basis of the availability of experimental data for comparison. Density functionals were examined with respect to their ability accurately to reproduce experimental properties, including, in particular, geometries and relative energies for the bis(mu-oxo) and side-on peroxo forms. While geometries from both hybrid and nonhybrid functionals were in good agreement with experiment, the incorporation of Hartree-Fock (HF) exchange in hybrid density functionals was found to have a large, degrading effect on predicted relative isomer energies. Specifically, hybrid functionals predicted the mu-eta(2):eta(2)-peroxo isomer to be too stable by roughly 5-10 kcal mol(-1) for each 10% of HF exchange incorporated into the model. Continuum solvation calculations predict electrostatic effects to favor bis(mu-oxo) isomers by 1-4 kcal mol(-1) depending on ligand size, with larger ligands having smaller differential solvation effects. Analysis of computed molecular partition functions suggests that nonzero measured entropies of isomerization are likely to be primarily associated with interactions between molecular solutes and their first solvation shell.
Lewin
John L
JL
Department of Chemistry and Supercomputer Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA,
Heppner
David E
DE
Cramer
Christopher J
CJ
D003300:Copper / Q000737:chemistry*; D008958:Models, Molecular; D010087:Oxides / Q000737:chemistry*; D013816:Thermodynamics
D010087:Oxides; D003300:Copper; C030973:cupric oxide
Dalton Trans. 2004 Dec 21;(24):4079-88
15573156
J Am Chem Soc. 2006 Mar 15;128(10):3445-58
16522125
J Am Chem Soc. 2003 Apr 30;125(17):5186-92
12708870
Inorg Chem. 2000 Sep 4;39(18):4059-72
11198861
Chem Rev. 2004 Feb;104(2):1047-76
14871149
Angew Chem Int Ed Engl. 2001 Dec 17;40(24):4570-4590
12404359
Inorg Chem. 2004 Jul 12;43(14):4115-7
15236520
J Am Chem Soc. 2002 Apr 24;124(16):4170-1
11960420
Angew Chem Int Ed Engl. 2002 Apr 2;41(7):1114-37
12491240
Inorg Chem. 2005 Oct 17;44(21):7345-64
16212361
J Phys Chem A. 2006 Oct 12;110(40):11557-68
17020270
Science. 1996 Mar 8;271(5254):1397-400
8596910
Chem Rev. 1996 Nov 7;96(7):2563-2606
11848837
J Biol Inorg Chem. 2003 May;8(5):577-85
12764603
Inorg Chem. 2006 May 1;45(9):3569-81
16634587
J Biol Inorg Chem. 2004 Sep;9(6):669-83
15311336
Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
9944570
Inorg Chem. 2006 Apr 3;45(7):3004-13
16562956
Inorg Chem. 2003 Dec 15;42(25):8534-44
14658910
Phys Rev Lett. 2003 Oct 3;91(14):146401
14611541
Phys Rev B Condens Matter. 1992 Jun 15;45(23):13244-13249
10001404
Inorg Chem. 1997 Oct 8;36(21):4831-4837
11670163
Inorg Chem. 2006 Jul 10;45(14):5239-41
16813375
J Phys Chem B. 2006 Aug 17;110(32):16066-81
16898764
J Phys Chem A. 2006 Feb 9;110(5):1991-2004
16451035
Inorg Chem. 1999 May 3;38(9):2161-2168
11671001
Phys Rev A Gen Phys. 1988 Sep 15;38(6):3098-3100
9900728
Chem Rev. 1996 Nov 7;96(7):2541-2562
11848836
Inorg Chem. 1998 Mar 23;37(6):1202-1212
11670324
Chem Rev. 2004 Feb;104(2):1013-45
14871148