The prediction of Fe Mössbauer parameters by the density functional theory: a benchmark study.
We report the performance of eight density functionals (B3LYP, BPW91, OLYP, O3LYP, M06, M06-2X, PBE, and SVWN5) in two Gaussian basis sets (Wachters and Partridge-1 on iron atoms; cc-pVDZ on the rest of atoms) for the prediction of the isomer shift (IS) and the quadrupole splitting (QS) parameters of Mössbauer spectroscopy. Two sources of geometry (density functional theory-optimized and X-ray) are used. Our data set consists of 31 iron-containing compounds (35 signals), the Mössbauer spectra of which were determined at liquid helium temperature and where the X-ray geometries are known. Our results indicate that the larger and uncontracted Partridge-1 basis set produces slightly more accurate linear correlations of electronic density used for the prediction of IS and noticeably more accurate results for the QS parameter. We confirm and discuss the earlier observation of Noodleman and co-workers that different oxidation states of iron produce different IS calibration lines. The B3LYP and O3LYP functionals have the lowest errors for either IS or QS. BPW91, OLYP, PBE, and M06 have a mixed success whereas SVWN5 and M06-2X demonstrate the worst performance. Finally, our calibrations and conclusions regarding the best functional to compute the Mössbauer characteristics are applied to candidate structures for the peroxo and Q intermediates of the enzyme methane monooxygenase hydroxylase (MMOH), and compared to experimental data in the literature.
Department of Chemistry, Columbia University, New York, New York 10027, and Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139.
Arteum D
AD
Bochevarov
Richard A
RA
Friesner
Stephen J
SJ
Lippard
Inorg Chem. 2009 Sep 7;48(17):8317-24
19642622
Inorg Chem. 2006 Oct 2;45(20):8297-307
16999430
J Chem Theory Comput. 2007 Jan;3(1):289-300
26627172
J Chem Phys. 2006 Jan 21;124(3):034108
16438568
J Phys Condens Matter. 2009 May 13;21(19):195501
21825488
J Comput Chem. 2006 Sep;27(12):1292-306
16786546
J Am Chem Soc. 2002 May 22;124(20):5890-4
12010064
J Am Chem Soc. 1986 Feb 1;108(3):557
22175507
J Am Chem Soc. 2006 Jun 14;128(23):7458-9
16756297
Chem Rev. 2003 Jun;103(6):2385-419
12797835
Phys Rev B Condens Matter. 1992 Sep 15;46(11):6671-6687
10002368
Chem Rev. 2004 Feb;104(2):987-1012
14871147
J Am Chem Soc. 2006 Mar 22;128(11):3528-9
16536520
Chem Rev. 2004 Feb;104(2):459-508
14871132
Angew Chem Int Ed Engl. 2002 Jan 4;41(1):149-52
12491468
Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
9944570
Dalton Trans. 2009 Aug 14;(30):6045-57
19623405
J Am Chem Soc. 2007 Mar 21;129(11):3135-47
17326634
Inorg Chem. 2003 Aug 25;42(17):5244-51
12924895
Inorg Chem. 2009 Oct 5;48(19):9155-65
19780615
Inorg Chem. 2005 Apr 4;44(7):2245-54
15792459
Angew Chem Int Ed Engl. 2001 Aug 3;40(15):2782-2807
29711993
J Am Chem Soc. 2008 Nov 19;130(46):15602-10
18939795
Inorg Chem. 2006 Sep 4;45(18):7050-2
16933901
Inorg Chem. 2008 Aug 18;47(16):7233-42
18646840
J Am Chem Soc. 2005 Nov 16;127(45):15778-90
16277521
J Am Chem Soc. 2002 Jul 3;124(26):7829-39
12083937
J Am Chem Soc. 2002 Nov 20;124(46):13921-30
12431124
J Am Chem Soc. 2001 Feb 7;123(5):827-38
11456616
J Am Chem Soc. 1976 Sep 1;98(18):5721-3
956577
J Comput Chem. 2007 Jan 30;28(2):555-69
17186489
J Am Chem Soc. 2004 Mar 10;126(9):2978-90
14995216
Inorg Chem. 2001 Aug 27;40(18):4617-22
11511206
J Chem Theory Comput. 2008 Feb;4(2):278-85
26620659
Inorganica Chim Acta. 2008 Mar 3;361(4):973-986
19262682
J Phys Chem A. 2009 Oct 29;113(43):11763-71
19572690
J Am Chem Soc. 2009 Sep 2;131(34):12155-71
19663382
J Chem Phys. 2009 Mar 28;130(12):124121
19334822
J Am Chem Soc. 2009 May 6;131(17):6074-5
19354250
Org Lett. 2006 Aug 17;8(17):3631-4
16898778
Inorg Chem. 1996 Nov 6;35(23):6892-6898
11666858
Phys Rev A Gen Phys. 1988 Sep 15;38(6):3098-3100
9900728
J Am Chem Soc. 2005 Mar 2;127(8):2505-13
15725005
J Chem Inf Model. 2007 May-Jun;47(3):1045-52
17428029
Phys Chem Chem Phys. 2010 Mar 20;12(11):2758-62
20200755
Phys Rev B Condens Matter. 1992 Jun 15;45(23):13244-13249
10001404
Inorg Chem. 2008 Apr 21;47(8):2975-86
18366153
Inorg Chem. 2009 Feb 2;48(3):784-5
19102678
Phys Rev Lett. 1996 Oct 28;77(18):3865-3868
10062328
Inorg Chem. 2002 Jul 1;41(13):3444-56
12079463
J Chem Phys. 2006 Sep 28;125(12):124107
17014166
Chem Rev. 2004 Feb;104(2):403-18
14871130
J Chem Phys. 2007 Aug 28;127(8):084101
17764223
J Chem Phys. 2008 Jan 21;128(3):034102
18205483
Proc Natl Acad Sci U S A. 2006 Nov 14;103(46):17107-12
17090681