Implicit and explicit coverage of multi-reference effects by densityfunctional theory

International Journal of Molecular Sciences

Volumn 3, Issue 6, 2002, Pages 604-638

  Cremer, Dieter ^a   Filatov, Michael ^a   Polo, Victor ^a   Kraka, Elfi ^a   Shaik, Sason ^b  

^a UNIVERSITY OF GOTHENBURG   (Sweden)

^b HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

CAS DFT; Ensemble theory; Exchange functional; Multi reference effects; Non dynamic electron correlation; REKS; Self interaction error; Two configurational DFT

Indexed keywords

HYDROGEN; RADICAL;

CALCULATION; CHEMICAL STRUCTURE; CORRELATION ANALYSIS; DENSITY FUNCTIONAL THEORY; ELECTRON; ERROR; MATHEMATICAL ANALYSIS; MOLECULE; REVIEW;

EID: 0000203986     PISSN: 14220067     EISSN: None     Source Type: Journal    
DOI: 10.3390/i3060604     Document Type: Review

References (113)

1. (a) Hohenberg, P.; Kohn, W. Inhomogeneous Electron Gas. Phys. Rev. 1964, 136, B 864-871.
2. (b) Kohn, W.; Sham, L. J. Self-Consistent Equations Including Exchange and Correlation Effects. Phys. Rev. 1965, 140, A 1133-1138.
3. Parr, R. G.; Yang, W. in International Series of Monographs on Chemistry 16: Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
4. A Chemist's Guide to Density Functional Theory, Koch W.; Holthausen M. C., Wiley-VCH: New York, 2001.
5. For reviews on DFT methods, see for example (a) Density Functional Methods in Chemistry, Labanowski, J. K.; Andzelm, J. W., Eds; Springer: Heidelberg, 1990.
6. (b) Theoretical and Computational Chemistry, Vol. 2, Modern Density Functional Theory - A Tool For Chemistry, Seminario, J. M.; Politzer, P., Eds.; Elsevier: Amsterdam, 1995.
7. (c) Chemical Applications of Density Functional Theory, ACS Symposium Series 629, Laird, B. B.; Ross, R. B.; Ziegler, T., Eds; American Chemical Society: Washington, DC, 1996.
8. (d) Lecture Notes in Physics, Density Functionals: Theory and Applications, Joubert, D., Ed.; Springer: Heidelberg, 1997.
9. (e) Recent Advances in Computational Chemistry, Vol. 1, Recent Advances in Density Functional Methods, Part II, Chong, D. P., Ed.; World Scientific: Singapore, 1997.
10. (f) Electronic Density Functional Theory, Recent Progress and New Directions, Dobson, J. F.; Vignale, G.; Das, M. P., Eds.; Plenum Press: New York, 1998.
11. (g) Gill, P. Density Functional Theory (DFT), Hartree-Fock (HF), and the Self-Consistent Field, in Encyclopedia of Computational Chemistry, Schleyer, P. v. R.; Allinger, N. L.; Clark, T.; Gasteiger, J.; Kollman, P. A.; Schaefer III, H. F.; Schreiner, P. R., Eds., Wiley: Chichester, UK, 1998, Vol. 1, p. 678-689.
12. 2 Theor. Chem. Acc. 1998, 99, 329-343.
13. 2 reactions J. Chem. Phys. 1999, 111, 4056-4067.
14. (a) Savin, A. Beyond the Kohn-Sham Determinant, in Recent Advances in Density Functional Methods, Part I, Chong, D. P., Ed.; World Scientific: Singapore, 1995, p. 123-153.
15. (b) Savin, A. On Degeneracy, Near Degeneracy and Density Functional Theory, in Recent Developments of Modern Density Functional Theory, Seminario, J. M., Ed; Elsevier, Amsterdam, 1996, 327-357.
16. Ziegler, T.; Rauk, A.; Baerends, E. J. On the calculation of multiplet energies by the Hartree-Fock-Slater method. Theor. Chim. Acta 1977, 43, 261-271.
17. von Barth, U. Local-density theory of multiplet structure Phys. Rev. A 1979, 20, 1693-1703.
18. Gräfenstein, J.; Kraka, E.; Filatov, M.; Cremer, D. Can Unrestricted Density-Functional Theory Describe Open Shell Singlet Biradicals? Int. J. Mol. Science, in press.
19. It has been pointed out that this statement is only correct when including ensemble DFT. See, Ref.s 5, 27, and 28.
20. Becke, A. D., Exchange-Correlation Approximations in Density-Functional Theory, in Advanced Series in Physical Chemistry, Vol. 2, Modern Electronic Structure Theory, Part II, Yarkony, D. R., Ed; World Scientific: Singapore, 1995, p. 1022-1046;
21. 2. J. Chem. Phys. 1997, 107, 5007-5015.
22. 2. Phys. Rev. A, 1998, 57, 1729-1742.
23. -: A Qualitative Rule To Predict Success or Failure of GGAs J. Phys. Chem. A, 2000, 104, 8558-8565.
24. d) Handy, N. C.; Cohen, A. J. Left-right correlation energy Mol. Phys., 2001, 99, 403-413.
25. Cremer, D.; Density Functional Theory - Coverage of Dynamic and Nondynamic Electron Correlation Effects Mol. Phys. 2001, 000-000.
26. (a) Polo, V.; Kraka, E.; Cremer, D. Nondynamic Electron Correlation and the Self-Interaction Error of Density Functional Theory Mol. Phys. (Davidson issue), 2002 in press.
27. (b) He, Y.; Gräfenstein, J.; Kraka, E.; Cremer, D. What Correlation Effects Are Covered by Density Functional Theory? Mol. Phys. 2000, 98, 1639-1658.
28. Polo, V.; Gräfenstein, J.; Kraka, E.; Cremer, D. Influence of the Self-Interaction Error on the Structure of the DFT Exchange Hole Chem. Phys. Lett., 2002, 352, 469-478.
29. Polo, V.; Kraka, E.; Cremer, D. Some Thoughts about the Stability and Reliability of Commonly Used Exchange-Correlation Functionals - Coverage of Dynamic and Nondynamic Correlation Effects Theoret. Chem. Accounts, 2002, in press.
30. Perdew, J.P.; Zunger, A. Self-interaction correction to density-functional approximations for many-electron systems. Phys. Rev. B 1981, 23, 5048-5079.
31. a) Perdew, J.P. In Local Density Approximations in Quantum Chemistry and Solid State Physics; Avery, J., Dahl, J.P., Eds.; New York: Plenum Press, 1984.
32. b) Perdew, J.P.; Ernzerhof, M. Driving out the self-interaction error. In Electronic Density Functional Theory: Recent Progress and New Directions; Dobson, J.F., Vignale, G., Das, M.P., Eds.; New York: Plenum Press, 1998; p. 31-41.
33. Harrison, J.G.; Heaton, R.A.; Lin, C.C. Self-interaction correction to the local density Hartree-Fock atomic calculations of excited and ground states. J. Phys. B: At. Mol. Phys. 1983, 16, 2079-2092.
34. a) Pederson, M.R.; Heaton, R.A.; Lin, C.C. Local-density Hartree-Fock theory of electronic states of molecules with self-interaction correction. J. Chem. Phys. 1984, 80, 1972-1982.
35. b) Pederson, M.R.; Heaton, R.A.; Lin, C.C. Density-functional theory with self-interaction correction: Application to the lithium molecule. J. Chem. Phys 1985, 82, 2688-2699.
36. Svane, A.; Temmerman, W.M.; Szotek, Z.; Laegsgaard, J.; Winter, H. Self-interaction-corrected local-spin-density calculations for rare earth materials. Int. J. Quantum Chem. 1999, 77, 799-813.
37. Goedecker, S.; Umrigar, C.J. Critical assessment of the self-interaction-corrected-local-density-functional method and its algorithmic implementation. Phys. Rev. A 1977, 55, 1765-1771.
38. a) Li, Y.; Krieger, J.B. Construction and application of gradient-expansion approximations for exchange energy with self-interaction correction. Phys. Rew. A 1990, 41, 1701-1704;
39. b) Chen, J.; Krieger, J.B.; Li, Y. Kohn-Sham calculations with self-interaction-corrected local-spin-density exchange-correlation energy functional for atomic systems. Phys. Rev. A 1996, 54, 3939-3947.
40. a) Garza, J.; Nichols, J.A.; Dixon, D.A. The optimized effective potential and the self-interaction correction in density functional theory: Application to molecules. J. Chem. Phys. 2000 112, 7880-7890.
41. b) Garza, J.; Nichols, J.A.; Dixon, D.A. The role of the local-multiplicative Kohn-Sham potential on the description of occupied and unoccupied orbitals. J. Chem. Phys. 2000, 113, 6029-6033.
42. c) Garza, J.; Vargas, R.; Nichols, J.A.; Dixon, D.A. Orbital energy analysis with respect to LDA and self-interaction corrected exchange-only potentials. J. Chem. Phys. 2001, 114, 639-651.
43. a) Guo, Y.; Whitehead, M.A. An alternative Self-interaction correction in the generalized exchange local-density functional theory. J. Comp. Chem. 1991, 12, 803-810.
44. b) Whitehead, M.A.; Suba, S. In Recent Advances in Computational Chemistry - Vol.1, Recent Advances in Density Functional Methods, Part I; Chong, D.P., Ed.; Singapore: World Scientific, 1995; p. 53-78.
45. Gill P.M.W.; Johnson B.G.; Gonzales C.A.; Pople J.A. A density functional study of the simplest hydrogen abstraction reaction. Effect of self-interaction correction. Chem. Phys. Lett. 1994, 221, 100-108.
46. Lieb, E. H. Density Functionals for Coulomb Systems. Int. J. Quantum Chem. 1983, 24, 243-277.
47. a) Englisch, H.; Englisch, R. Exact Density Functionals for Ground-State Densities. I. General Results Phys. Stat. Sol (b) 1984, 123, 711-721.
48. b) Englisch, H.; Englisch, R. Exact Density Functionals for Ground-State Densities. II. Details and Remarks Phys. Stat. Sol (b) 1984, 124, 373-379.
49. c) Levy, M. Electron densities in search of Hamiltonians Phys. Rev. A 1982, 26, 1200-1208.
50. a) Filatov, M.; Shaik, S. A spin-restricted ensemble-referenced Kohn-Sham method and its application to diradicaloid situations. Chem. Phys. Lett. 1999, 304, 429-437;
51. b) Filatov, M.; Shaik, S. Artificial symmetry breaking in radicals is avoided by the use of the Ensemble-Referenced Kohn-Sham (REKS) method Chem. Phys. Lett. 2000, 332, 409-419.
52. a) Filatov, M.; Shaik, S. Tetramethyleneethane (TME) Diradical: Experiment and Density Functional Theory Reach an Agreement J. Phys. Chem. A 1999, 103, 8885-8889;
53. b) Filatov, M.; Shaik, S.; Woeller, M.; Grimme, S; Peyerimhoff, S. Locked alkenes with a short triplet state lifetime Chem. Phys. Lett. 2000, 316, 135-140;
54. c) Filatov, M.; Shaik, S. Diradicaloids: Description by the Spin-Restricted Ensemble-Referenced Kohn-Sham Density Functional Method J. Phys. Chem. A 2000, 104, 6628-6636;
55. d) Filatov, M.; Shaik, S.; de Visser, S. P. REKS calculations on ortho-, meta- and para-benzyne Phys. Chem. Chem. Phys. 2000, 2, 5046-5048;
56. e) Filatov, M.; Shaik, S.; de Visser, S. P. Myers-Saito and Schmittel cyclization of hepta-1,2,4-triene-6-yne: A theoretical REKS study Phys. Chem. Chem. Phys. 2001, 3, 1242-1245.
57. (a) Kraka, E. Homolytic dissociation-energies from GVB-LSDC calculations. Chem. Phys. 1992, 161, 149-153.
58. (b) Kraka, E.; Cremer, D.; Nordholm, S.A New Way of Calculating Bond Dissociation Energies, in Molecules in Natural Science and Biomedicine; Maksic, Z., Eckert-Maksic, M., Eds.; Ellis Horwood, Chichester, 1991; p. 351-374.
59. (c) In the case of the OSS state of 1 or 2, the GVB-DFT description simplifies to a ROHF-DFT description. See, Davidson, E. R. Spin-restricted open-shell self-consistent-field theory. Chem. Phys. Lett. 1973, 21, 565-567.
60. (a) Gräfenstein, J; Cremer, D. The combination of density functional theory with multi-configuration methods - CAS-DFT. Chem. Phys. Lett. 2000, 316, 569-577.
61. (b) Gräfenstein, J.; Cremer, D. Can density functional theory describe multi-reference systems? Investigation of carbenes and organic biradicals. Phys. Chem. Chem. Phys. 2000, 2, 2091-2103.
62. Gräfenstein, J.; Cremer, D.; Kraka, E. Density functional theory for open-shell singlet biradicals. Chem. Phys. Lett. 1998, 288, 593-602.
63. a) Filatov, M.; Shaik, S. Spin-restricted density functional approach to the open-shell problem. Chem. Phys. Lett. 1998, 288, 689-697;
64. b) Filatov, M.; Shaik, S. Application of spin-restricted open-shell Kohn-Sham method to atomic and molecular multiplet states. J. Chem. Phys. 1999, 110, 116-125.
65. Dunning Jr., T. H. Gaussian-basis sets for use in correlated molecular calculations. 1. The atoms boron through neon and hydrogen. J. Chem. Phys. 1989, 90, 1007-1023.
66. Slater, J. C. A Simplification of the Hartree-Fock Method Phys. Rev. 1951, 81, 385-390.
67. Vosko, S. H.; Wilk, L.; Nusair, M. Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Can J. Phys. 1980, 58, 1200-1211.
68. Polo, V.; Kraka, E.; Cremer, D., to be published.
69. See, e.g., Baerends, E. J.; Gritsenko, O. V. A Quantum Chemical View of Density Functional Theory. J. Phys. Chem. A, 1997, 101, 5383-5403.
70. Note that there is also a difference between VWN5 correlation and SIC-VWN5 correlation, [14b,15,16] which is not considered in this work.
71. (a) Langreth, D. C.; Perdew, J. P. The exchange correlation energy of a metallic surface. Solid State Commun. 1975, 17, 1425-1429.
72. (b) Gunnarsson, O.; Lundqvist, B. I. Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism. Phys. Rev. B 1976, 13, 4274-98.
73. Harris, J. Adiabatic connection approach to Kohn-Sham theory Phys. Rev. A 1998, 288, 689-697.
74. Hariharan, P. C.; Pople, J. A. The Influence of Polarization Functions on Molecular Orbital Hydrogenation Energies. Theor. Chim. Acta 1973, 28, 213-222.
75. Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic-behavior. Phys. Rev. A 1988, 38, 3098-3100.
76. Lee, C.; Yang, W.; Parr, R. P. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron-density. Phys. Rev. B 1988, 37, 785-789.
77. (a) Becke, A. D. Density-functional thermochemistry. 3. The role of exact exchange. J. Chem. Phys. 1993, 98, 5648-5652.
78. See also (b) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. Ab-initio calculation of vibrational absorption and circular-dichroism spectra using density-functional force-fields. J. Phys. Chem. 1994, 98, 11623-11627.
79. Becke, A. D. A new mixing of HartreeFock and local density-functional theories J. Chem. Phys. 1993, 98, 1372-1377.
80. a) Perdew, J. P., in Electronic Structure of Solids '91, Ziesche, P.; Eschrig, H., Eds. Akademie-Verlag: Berlin, 1991, p. 11.
81. b) Perdew, J. P. and Wang, Y., Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 1992, 45, 13244-13249.
82. a) Colle, R.; Salvetti, O. Approximate calculation of the correlation energy for the closed shells Theor. Chim. Acta 1975, 37, 329-334.
83. b) Colle, R.; Salvetti, O. Generalization of the Colle-Salvetti correlation-energy method to a many-determinant wave-function J. Chem. Phys. 1990, 93, 534-544.
84. Kraka, E.; Gräfenstein, J.; Gauss, J.; Filatov, M.; Polo, V.; Reichel, F.; Olsson, L.; Konkoli, Z; He, Z; Cremer, D. COLOGNE2001, Göteborg University, Göteborg, 1999.
85. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, Jr., J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.5, Gaussian, Inc., Pittsburgh PA, 1998.
86. (a) Kraka, E.; Cremer, D. CCSD(T) investigation of the Bergman cyclization of enediyne - Relative stability of o-didehydrobenzene, m-didehydrobenzene, and p-didehydrobenzene. J. Am. Chem. Soc. 1994, 116, 4929-4936.
87. (b) Kraka, E.; Cremer, D. Ortho-benzyne, meta-benzyne, and para-benzyne - A comparative CCSD(T) investigation. Chem. Phys. Lett. 1993, 216, 333-340.
88. Gräfenstein, J.; Hjerpe, A. M.; Kraka, E.; Cremer, D. An accurate description of the Bergman reaction using restricted and unrestricted DFT: Stability test, spin density, and on-top pair density. J. Phys. Chem. A, 2000, 104, 1748-1761.
89. Kraka, E.; Cremer, D. The para-didehydropyridine, para- didehydropyridinium, and related biradicals - A contribution to the chemistry of enediyne antitumor drugs. J. Comp. Chem. 2001, 22, 216-229.
90. Kraka, E.; Cremer, D. Computer design of anticancer drugs. A new enediyne warhead. J. Am. Chem. Soc. 2000, 122, 8245-8264.
91. Crawford, T. D.; Kraka, E.; Stanton, J. F.; Cremer, D. Problematic p-Benzyne: Orbital Instabilities, Biradical Character, and Broken Spin Symmetry. J. Chem. Phys. 2001, 114, 10638-10650.
92. Kraka, E.; Cremer, D.; Bucher, G.; Wandel, H.; Sander, W. A CCSD(T) and DFT investigation of m-benzyne and 4-hydroxy-m-benzyne. Chem. Phys. Lett. 1997, 268, 313-320.
93. Kraka, E.; Anglada, J.; Hjerpe, A.; Filatov, M.; Cremer, D. m-Benzyne and Bicyclo[3.1.0]hexatriene - Which Isomer is more Stable? - A Quantum Chemical Investigation. Chem. Phys. Lett. 2001, 348, 115-125.
94. Winkler, M.; Sander, W. The Structure of meta-Benzyne Revised - A Close Look into s-Bond Formation. J. Phys. Chem. A 2001, 105, 10422-10432.
95. Wenthold, P. G.; Squires, R. R.; Lineberger, W. C. Ultraviolet Photoelectron Spectroscopy of the o-, m-, and p- Benzyne Negative Ions. Electron Affinities and Singlet-Triplet Splittings for o-, m-, and p- Benzyne. J. Am. Chem. Soc. 1998, 120, 5279-5290.
96. a) Wierschke, S. G.; Nash, J. J; A multiconfigurational SCF and correlation-consistent CI study of the structures, stabilities, and singlet-triplet splittings of o-benzyne, m-benzyne, and p-benzyne. Squires, R. R., J. Am. Chem. Soc. 1993, 115, 11958-11967.
97. b) Wenthold, P. G.; Paulino, J. A.; Squires, R. R. The absolute heats of formation of ortho-benzyne, meta-benzyne, and para-benzyne. J. Am. Chem. Soc. 1991, 113, 7414-7415.
98. c) Wenthold, P. G.; Squires, R. R. Biradical thermochemistry from collision-induced dissociation threshold energy measurements - Absolute heats of formation of ortho-benzyne, meta-benzyne, and para-benzyne. J. Am. Chem. Soc. 1994, 116, 6401-6412.
99. Skancke, A.; Hrovat, D. A.; Borden W. T. Ab initio calculations of the effects of geminal silyl substituents on the stereomutation of cyclopropane and on the singlet-triplet splitting in trimethylene. J. Am. Chem. Soc., 1998, 120, 7079-7084.
100. For a recent review, see Bally, T.; Borden, W. T. Calculations on Open Shell Molecules: A Beginner's Guide, in Reviews Comp. Chem. Lipkowitz, K. B.; Boyd, D. B., Eds.; Wiley: New York, 1999; Vol. 13, p. 1-97.
101. Roth, W. R.; Kowalczik, U.; Maier, G.; Reisenauer, H. P.; Sustmann, R.; Müller, W. 2,2-dimethyl-4,5-dimethylene-1,3-cyclopentanediyl Angew. Chem. Int. Ed. Engl. 1987, 26, 1285-1287.
102. Nash, J. J.; Dowd, P.; Jordan, K. D. Theoretical study of the low-lying triplet and singlet states of diradicals: prediction of ground-state multiplicities in cyclic analogues of tetramethyleneethane J. Am. Chem. Soc. 1992, 114, 10071-10072.
103. Zilm, K. W.; Merill, R. A.; Greenberg, M. M.; Berson, J. A. The first magic angle spinning NMR spectrum of a captive intermediate: Direct observation of a singlet ground state biradical, 3,4-dimethylenefuran J. Am. Chem. Soc. 1987, 109, 1567-1569.
104. See, e.g., a) Werner, H.-J. Matrix-Formulated Direct Multiconfiguration Self-Consistent Field and Multiconfiguration Reference Configuration-Interaction Methods in sl Advances in Chemical Physics, Volume LXIX, Ab Initio Methods in Quantum Chemistry, Part II, Lawlay, K. P., Ed.; Wiley: New York, 1987, p. 1-62.
105. b) Shepard, R. The Multiconfiguration Self-Consistent Field Method, in sl Advances in Chemical Physics, Volume LXIX, Ab Initio Methods in Quantum Chemistry, Part II, Lawlay, K. P., Ed.; Wiley: New York, 1987, p. 63-200.
106. c) Szalay, P. G. Towards State-Specific Formulation of Multireference Coupled-Cluster Theory, in Modern Ideas in Coupled-Cluster Methods, Bartlett, R. J. Ed.; World Scientific: Singapore, 1997; p. 81-123.
107. Borowski, P.; Jordan, K. D.; Nichols, J.; Nachtigall P. Investigation of a hybrid TCSCF-DFT procedure Theor. Chem. Acc. 1998, 99, 135-140.
108. Grimme, S.; Waletzke, M. A combination of Kohn Sham density functional theory and multi-reference configuration interaction methods J. Phys. Chem. 1999, 111, 5645-5655.
109. Pollet, R.; Savin, A.; Leininger, T.; Stoll, H. Combining multideterminantal wave functions with density functionals to handle near-degeneracy in atoms and molecules J. Phys. Chem. 2002, 116, 1250-1258.
110. a) Miehlich, B.; Stoll, H.; Savin, A. A correlation-energy density functional for multideterminantal wavefunctions. Mol. Phys., 1997, 3, 527-536.
111. b) Savin, A. Int. J. Quant. Chem. Symp. 1988, 22, 59.
112. Moscardò, F.; SanFabiàn E. Density-functional formalism and the two-body problem Phys. Rev. 1991, A 44, 1549-1553.
113. Gräfenstein, J.; Cremer, D., to be published.