Accurate magnetic exchange couplings in transition-metal complexes from constrained density-functional theory
10.1063/1.2145878
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

We demonstrate an accurate method for extracting Heisenberg exchange-coupling constants (J) from density-functional theory (DFT) calculations. We note that the true uncoupled low-spin state of a given molecule should be identified with the ground state of the system subject to a constraint on the spin density of the atoms. Using an efficient optimization strategy for constrained DFT we obtain these states directly, leading to a simple, physically motivated formula for J. Our method only depends on state energies and their associated electron densities and assigns no unphysical meaning to the Kohn-Sham determinant or individual orbitals. We study several bimetallic transition-metal complexes and find that the constrained DFT approach is competitive with, if not better than, the best broken symmetry DFT results. The success of constrained DFT in these cases appears to result from a balanced elimination of self-interaction error and static correlation from the simulation.

Bibliography

Rudra, I., Wu, Q., & Van Voorhis, T. (2006). Accurate magnetic exchange couplings in transition-metal complexes from constrained density-functional theory. The Journal of Chemical Physics, 124(2).

Authors 3
  1. Indranil Rudra (first)
  2. Qin Wu (additional)
  3. Troy Van Voorhis (additional)
References 61 Referenced 106
  1. 10.1002/anie.199100341 / Angew. Chem., Int. Ed. Engl. (1991)
  2. {'volume-title': 'Molecular Magnetism: From Molecular Assemblies to the Devices', 'year': '1995', 'author': 'Coronado', 'key': '2023063020192120800_c2'} / Molecular Magnetism: From Molecular Assemblies to the Devices by Coronado (1995)
  3. {'key': '2023063020192120800_c3', 'first-page': '66', 'volume': '25', 'year': '2000', 'journal-title': 'MRS Bull.'} / MRS Bull. (2000)
  4. {'volume-title': 'Molecular Magnetism', 'year': '1993', 'key': '2023063020192120800_c4'} / Molecular Magnetism (1993)
  5. 10.1063/1.1446024 / J. Chem. Phys. (2002)
  6. 10.1103/PhysRev.140.A1133 / Phys. Rev. (1965)
  7. 10.1016/0009-2614(79)85043-5 / Chem. Phys. Lett. (1999)
  8. 10.1063/1.440939 / J. Chem. Phys. (1981)
  9. 10.1021/ja00298a004 / J. Am. Chem. Soc. (1985)
  10. 10.1016/0009-2614(94)01221-0 / Chem. Phys. Lett. (1994)
  11. {'key': '2023063020192120800_c11', 'first-page': '625', 'volume': '4', 'year': '1986', 'journal-title': 'Chem. Lett.'} / Chem. Lett. (1986)
  12. 10.1021/ja00320a017 / J. Am. Chem. Soc. (1984)
  13. 10.1016/S0898-8838(08)60070-7 / Adv. Inorg. Chem. (1992)
  14. 10.1063/1.1430740 / J. Chem. Phys. (2002)
  15. 10.1002/(SICI)1096-987X(199910)20:13<1391::AID-JCC6>3.0.CO;2-J / J. Comput. Chem. (1999)
  16. 10.1021/ic970310r / Inorg. Chem. (1997)
  17. 10.1021/ja981661n / J. Am. Chem. Soc. (1998)
  18. 10.1021/ic011308+ / Inorg. Chem. (2002)
  19. 10.1002/jcc.10257 / J. Comput. Chem. (2003)
  20. 10.1021/jp962091l / J. Phys. Chem. A (1997)
  21. 10.1016/S0009-2614(00)00166-4 / Chem. Phys. Lett. (2000)
  22. 10.1103/PhysRevLett.53.2512 / Phys. Rev. Lett. (1984)
  23. 10.1039/a909905k / Phys. Chem. Chem. Phys. (2000)
  24. 10.1103/PhysRev.97.1474 / Phys. Rev. (1955)
  25. 10.1063/1.1407276 / J. Chem. Phys. (2001)
  26. 10.1103/PhysRevA.72.024502 / Phys. Rev. A (2005)
  27. {'year': '2004', 'key': '2023063020192120800_c27'} (2004)
  28. 10.1063/1.1545679 / J. Chem. Phys. (2003)
  29. 10.1063/1.1821494 / J. Chem. Phys. (2004)
  30. 10.1063/1.464913 / J. Chem. Phys. (1993)
  31. 10.1021/ja961199b / J. Am. Chem. Soc. (1997)
  32. 10.1063/1.463096 / J. Chem. Phys. (1992)
  33. 10.1063/1.467146 / J. Chem. Phys. (1994)
  34. 10.1063/1.1999631 / J. Chem. Phys. (2005)
  35. {'key': '2023063020192120800_c35'}
  36. 10.1039/b102346m / J. Chem. Soc. Dalton Trans. (2001)
  37. 10.1021/ic50171a023 / Inorg. Chem. (1977)
  38. 10.1021/ic00071a015 / Inorg. Chem. (1993)
  39. 10.1021/ic971549a / Inorg. Chem. (1998)
  40. 10.1021/ic00057a006 / Inorg. Chem. (1993)
  41. 10.1021/ja0390202 / J. Am. Chem. Soc. (2004)
  42. 10.1021/ic00102a033 / Inorg. Chem. (1994)
  43. 10.1021/ic00105a027 / Inorg. Chem. (1995)
  44. 10.1021/ic00096a025 / Inorg. Chem. (1994)
  45. 10.1016/j.theochem.2003.10.041 / J. Mol. Struct.: THEOCHEM (2004)
  46. 10.1002/(SICI)1521-3765(19980310)4:3<476::AID-CHEM476>3.0.CO;2-8 / Chem.-Eur. J. (1998)
  47. 10.1021/ja961545p / J. Am. Chem. Soc. (1996)
  48. 10.1021/jp001908e / J. Phys. Chem. A (2000)
  49. 10.1002/ejic.200300493 / Eur. J. Inorg. Chem. (2004)
  50. 10.1002/ejic.200300336 / Eur. J. Inorg. Chem. (2003)
  51. 10.1021/ja0390202 / J. Am. Chem. Soc. (2004)
  52. 10.1063/1.2085171 / J. Chem. Phys. (2005)
  53. 10.1007/s00214-002-0331-4 / Theor. Chem. Acc. (2002)
  54. 10.1021/jp0204410 / J. Phys. Chem. A (2002)
  55. 10.1103/PhysRevB.23.5048 / Phys. Rev. B (1981)
  56. {'key': '2023063020192120800_c56'}
  57. 10.1016/0009-2614(94)87024-1 / Chem. Phys. Lett. (1994)
  58. 10.1016/0009-2614(94)01221-0 / Chem. Phys. Lett. (1994)
  59. 10.1103/PhysRevLett.65.1148 / Phys. Rev. Lett. (1990)
  60. 10.1103/PhysRevB.69.132502 / Phys. Rev. B (2004)
  61. 10.1016/S0009-2614(98)00364-9 / Chem. Phys. Lett. (1998)
Dates
Type When
Created 19 years, 7 months ago (Jan. 6, 2006, 6:05 p.m.)
Deposited 2 years, 1 month ago (June 30, 2023, 4:19 p.m.)
Indexed 4 weeks, 1 day ago (July 30, 2025, 6:46 a.m.)
Issued 19 years, 7 months ago (Jan. 10, 2006)
Published 19 years, 7 months ago (Jan. 10, 2006)
Published Online 19 years, 7 months ago (Jan. 10, 2006)
Published Print 19 years, 7 months ago (Jan. 14, 2006)
Funders 0

None

@article{Rudra_2006, title={Accurate magnetic exchange couplings in transition-metal complexes from constrained density-functional theory}, volume={124}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.2145878}, DOI={10.1063/1.2145878}, number={2}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Rudra, Indranil and Wu, Qin and Van Voorhis, Troy}, year={2006}, month=jan }