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Finding the Reactive Electron in Paramagnetic Systems: A Critical Evaluation of Accuracies for EPR Spectroscopy and Density Functional Theory Using 1,3,5-Triphenyl Verdazyl Radical as a Testcase

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Abstract

One of the biggest challenges in studying catalytic reactions is characterizing intermediate states and identifying reaction pathways. Oftentimes, intermediate states with unpaired electrons are formed which provide an opportunity to study the compound via electron paramagnetic resonance (EPR). Combining EPR with density functional theory (DFT) represents a powerful synergistic approach to accomplish these goals. Once the catalytic intermediates and reaction pathway are known, rate-limiting steps critical to parameters like overpotential and turnover number may be identified and eliminated. In this study 1,3,5-triphenyl verdazyl is examined using continuous-wave-EPR, electron nuclear double resonance and DFT as an instructive example of how theory and experiment can complement each other to find the reactive electron. The methods and concomitant analysis have been presented in didactic fashion and with emphasis on the strengths and weaknesses of the methods.

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References

  1. A.J. Stone, Proc. R. Soc. Lond. Ser. A 271, 424–434 (1963)

    Article  ADS  MATH  Google Scholar 

  2. A. Schweiger, G. Jeschke, Principles of Pulse Electron Paramagnetic Resonance (Oxford University Press, Oxford, 2001)

    Google Scholar 

  3. A. Carrington, A.D. McLachlan, Introduction to Magnetic Resonance (Harper & Row, New York, 1969)

    Google Scholar 

  4. G.E. Pake, T.L. Estle, The Physical Principles of Electron Paramagnetic Resonance (Benjamin-Cummings Publishing Company, Menlo Park, 1973)

    Google Scholar 

  5. J.E. Harriman, Theoretical Foundations of Electron Spin Resonance (Academic Press, New York, 1978)

    Google Scholar 

  6. R. McWeeny, Spins in Chemistry (Dover Publications Inc., New York, 2013)

    Google Scholar 

  7. P.M.W. Gill, in Encyclopedia of Computational Chemistry, ed. by P. von Ragué Schleyer (Wiley, Chichester, 1998), pp. 678–689

  8. F. Neese, Wiley Interdiscip. Rev. Comput. Mol. Sci. 2, 73–78 (2012)

  9. M.W. Schmidt, K.K. Baldridge, J.A. Boatz, S.T. Elbert, M.S. Gordon, J.H. Jensen, S. Koseki, N. Matsunaga, K.A. Nguyen, S.J. Su, T.L. Windus, M. Dupuis, J.A. Montgomery, J. Comput. Chem. 14, 1347–1363 (1993)

    Article  Google Scholar 

  10. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Peterson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishuda, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Kelene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyav, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, in (Gaussian Inc, Wallingford CT, 2004)

  11. M. Valiev, E.J. Bylaska, N. Govind, K. Kowalski, T.P. Straatsma, H.J.J. van Dam, D. Wang, J. Nieplocha, E. Apra, T.L. Windus, W.A. de Jong, Comput. Phys. Commun. 181, 1477–1489 (2010)

    Article  ADS  MATH  Google Scholar 

  12. Turbomole GmbH, Turbomole, available from http://www.turbomole.com, in Turbomole GmbH, Mannheim (2014)

  13. H.-J. Werner, P.J. Knowles, G. Knizia, F.R. Marnby, M. Schütz, P. Celani, T. Korona, R. Lindh, A. Mitrushenkov, G. Rauhut, K.R. Shamasundar, 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, A. Hesselmann, G. Hetzer, T. Hrenar, G. Jansen, C. Köppl, Y. Liu, A.W. Lloyd, R.A. Mata, A.J. May, S.J. McNicholas, W. Meyer, M.E. Mura, D.P. Nicklass, D.P. O’Neill, P. Palmieri, D. Peng, K. Pflüger, R. Pitzer, M. Reiher, T. Shiozaki, H. Stoll, A.J. Stone, R. Tarroni, T. Thorsteinsson, M. Wang, MOLPRO, a package of ab initio programs, in (2012)

  14. F. Aquilante, L. De Vico, N. Ferré, G. Ghigo, P.-A. Malmqvist, P. Neogrády, T.B. Pedersen, M. Pitonak, M. Reiher, B.O. Roos, L. Serrano-Andrés, M. Urban, V. Veryazov, R. Lindh, J. Comput. Chem. 31, 224–247 (2010)

    Article  Google Scholar 

  15. SCM Scientific Computing and Modelling, ADF, in SCM, Theoretical Chemistry (Vrije Universiteit Amsterdam, the Netherlands, 2013)

  16. R. Kuhn, H. Trischmann, Monatsh. Chem. 95, 457–479 (1963)

    Article  Google Scholar 

  17. The Mathworks GmbH, MATLAB and Statistics Toolbox, in The Mathworks Inc, Natic, Massachusetts (2012)

  18. S. Stoll, A. Schweiger, J. Magn. Reson. 178, 42–55 (2006)

    Article  ADS  Google Scholar 

  19. C.T. Lee, W.T. Yang, R.G. Parr, Phys. Rev. B 37, 785–789 (1988)

    Article  ADS  Google Scholar 

  20. F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 7, 3297–3305 (2005)

    Article  Google Scholar 

  21. R. Izsak, F. Neese, J. Chem. Phys. 135, 144105 (2011)

    Article  ADS  Google Scholar 

  22. J.P. Perdew, Phys. Rev. B 33, 8822–8824 (1986)

    Article  ADS  Google Scholar 

  23. A.D. Becke, Phys. Rev. A 38, 3098–3100 (1988)

    Article  ADS  Google Scholar 

  24. W. Kutzelnigg, U. Fleischer, M. Schindler, The IGLO-Method: ab initio Calculation and Interpretation of NMR Chemical Shifts and Magnetic Susceptibilities (Springer-Verlag, Heidelberg, 1990)

    Google Scholar 

  25. F. Neese, J. Chem. Phys. 118, 3939–3948 (2003)

    Article  ADS  Google Scholar 

  26. F. Neese, J. Phys. Chem. A 105, 4290–4299 (2001)

    Article  Google Scholar 

  27. H.M. McConnell, D.B. Chesnut, J. Chem. Phys. 28, 107–117 (1958)

    Article  ADS  Google Scholar 

  28. G.K. Woodgate, Elementary Atomic Structure (Oxford University Press, Oxford, 1983)

    Google Scholar 

  29. A. Szabo, N.S. Ostlund, Modern Quantum Chemistry. Introduction to Advanced Electronic Structure Theory (McGraw-Hill, New York, 1989)

    Google Scholar 

  30. T. Yonezawa, T. Kawamura, H. Kato, J. Chem. Phys. 50, 3482–3492 (1969)

    Article  ADS  Google Scholar 

  31. Bruker Biospin GmbH, Bruker EPR/ENDOR frequency table, in Bruker Biospin GmbH (2013)

  32. P.W. Atkins, Molecular Quantum Mechanics (Oxford University Press, Oxford, 2005)

    Google Scholar 

  33. G.A. Zhurko, Chemcraft v. 1.7, available at www.chemcraftprog.org, in (2014)

  34. R. Dennington, T. Keith, J.M. Millam, Gaussview, in Shawnee Mission KS (2009)

  35. W.J. Hehre, R. Ditchfie, J.A. Pople, J. Chem. Phys. 56, 2257–2261 (1972)

    Article  ADS  Google Scholar 

  36. P.C. Harihara, J.A. Pople, Theoret. Chim. Acta 28, 213–222 (1973)

    Article  Google Scholar 

  37. L. Hermosilla, J.M. Garcia de la Vega, C. Sieiro, P. Calle, J. Chem. Theory Comput. 7, 169–179 (2011)

    Article  Google Scholar 

  38. T.H. Dunning, J. Chem. Phys. 90, 1007–1023 (1989)

    Article  ADS  Google Scholar 

  39. J.M. Tao, J.P. Perdew, V.N. Staroverov, G.E. Scuseria, Phys. Rev. Lett. 91, 146401 (2003)

    Article  ADS  Google Scholar 

  40. A.D. Becke, J. Chem. Phys. 98, 5648–5652 (1993)

    Article  ADS  Google Scholar 

  41. L. Hermosilla, P. Calle, J.M.G. de la Vega, C. Sieiro, J. Phys. Chem. A 109, 1114–1124 (2005)

    Article  Google Scholar 

  42. L. Hermosilla, P. Calle, J.M.G. de la Vega, C. Sieiro, J. Phys. Chem. A 110, 13600–13608 (2006)

    Article  Google Scholar 

  43. H.F. Hameka, A.G. Turner, J. Magn. Reson. 64, 66–75 (1985)

    ADS  Google Scholar 

  44. N. Rega, M. Cossi, V. Barone, J. Chem. Phys. 105, 11060–11067 (1996)

    Article  ADS  Google Scholar 

  45. V. Barone, J. Phys. Chem. 99, 11659–11666 (1995)

    Article  Google Scholar 

  46. V. Barone, in Recent Advances in Density Functional Methods, Part I, ed. by D.P. Chong (World Scientific Publishing Company, Singapore, 1996)

  47. T. Enevoldsen, J. Oddershede, S.P.A. Sauer, Theor. Chem. Acc. 100, 275–284 (1998)

    Article  Google Scholar 

  48. P.F. Provasi, G.A. Aucar, S.P.A. Sauer, J. Chem. Phys. 115, 1324–1334 (2001)

    Article  ADS  Google Scholar 

  49. R.A. Kendall, T.H. Dunning, R.J. Harrison, J. Chem. Phys. 96, 6796–6806 (1992)

    Article  ADS  Google Scholar 

  50. Y. Zhao, D.G. Truhlar, Theor. Chem. Acc. 120, 215–241 (2008)

    Article  Google Scholar 

  51. V.N. Staroverov, G.E. Scuseria, J.M. Tao, J.P. Perdew, J. Chem. Phys. 119, 12129–12137 (2003)

    Article  ADS  Google Scholar 

  52. V.N. Staroverov, G.E. Scuseria, J.M. Tao, J.P. Perdew, J. Chem. Phys. 121, 11507 (2004)

    Article  ADS  Google Scholar 

  53. Y.-S. Lin, G.-D. Li, S.-P. Mao, J.-D. Chai, J. Chem. Theory Comput. 9, 263–272 (2013)

    Article  Google Scholar 

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Acknowledgments

We thank Annette Schäfermeier (University of Bonn) for her help with the synthesis of 1,3,5-triphenyl verdazyl. We also thank Dr. Ragnar Björnsson for many helpful conversations regarding computational approaches. This project was funded by the Max Planck Institute for Chemical Energy Conversion.

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  1. Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany

    Jessica Barilone, Frank Neese & Maurice van Gastel

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  1. Jessica Barilone
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  2. Frank Neese
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Correspondence to Maurice van Gastel.

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723_2014_627_MOESM1_ESM.docx

Electronic Supplementary Information (ESI) available: cartesian coordinates [Å] or the model geometries used in the calculations, Mulliken charge and spin populations and singly occupied molecular orbital. (DOCX 81 kb)

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Barilone, J., Neese, F. & van Gastel, M. Finding the Reactive Electron in Paramagnetic Systems: A Critical Evaluation of Accuracies for EPR Spectroscopy and Density Functional Theory Using 1,3,5-Triphenyl Verdazyl Radical as a Testcase. Appl Magn Reson 46, 117–139 (2015). https://doi.org/10.1007/s00723-014-0627-2

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