Abstract
The extended Koopmans’ theorem is related to Fukui function, which measures the change in electron density that accompanies electron attachment and removal. Two approaches are used, one based on the extended Koopmans’ theorem differential equation and the other based directly on the expression of the ionized wave function from the extended Koopmans’ theorem. It is observed that the Fukui function for electron removal can be modeled as the square of the first Dyson orbital, plus corrections. The possibility of useful generalizations to the extended Koopmans’ theorem is considered; some of these extensions give approximations, or even exact expressions, for the Fukui function for electron attachment.
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Parr RG, Yang W (1989) Density-functional theory of atoms and molecules. Oxford UP, New York
Geerlings P, De Proft F, Langenaeker W (2003). Chem Rev 103:1793
Ayers PW, Anderson JSM, Bartolotti LJ (2005). Int J Quantum Chem 101:520
Bartolotti LJ, Ayers PW (2005). J Phys Chem A 109:1146
Flurchick K, Bartolotti L (1995). J Mol Graph 13:10
Langenaeker W, Demel K, Geerlings P (1991). Theochem 80:329
Gritsenko OV, Ensing B, Schipper PRT, Baerends EJ (2000). J Phys Chem A 104:8558
Zhang Y, Yang W (1998). J Chem Phys 109:2604
Parr RG, Donnelly RA, Levy M, Palke WE (1978). J Chem Phys 68:3801
Parr RG, Pearson RG (1983). J Am Chem Soc 105:7512
Perdew JP, Parr RG, Levy M, Balduz JL Jr. (1982). Phys Rev Lett 49:1691
Zhang Y, Yang W (2000). Theor Chem Acc 103:346
Yang W, Zhang Y, Ayers PW (2000). Phys Rev Lett 84:5172
Gyftopoulos EP, Hatsopoulos GN (1965). Proc Natl Acad Sci USA 60:786
Chan GKL (1999). J Chem Phys 110:4710
Parr RG, Von Szentpaly L, Liu SB (1999). J Am Chem Soc 121:1922
Ayers PW, Anderson JSM, Rodriguez JI, Jawed Z (2005). Phys Chem Chem Phys 7:1918
Politzer P, Truhlar D (1981). Chemical applications of atomic and molecular electrostatic potentials. Plenum, New York
Ayers PW, Parr RG (2001). J Am Chem Soc 123:2007
Yang W, Parr RG, Pucci R (1984). J Chem Phys 81:2862
Parr RG, Yang W (1984). J Am Chem Soc 106:4049
Ayers PW, Levy M (2000). Theor Chem Acc 103:353
Ghanty TK, Ghosh SK (1994). J Am Chem Soc 116:3943
Galvan M, Vela A, Gazquez JL (1988). J Phys Chemi 92:6470
Melin J, Aparicio F, Galvan M, Fuentealba P, Contreras R (2003). J Phys Chem A 107:3831
Chamorro E, De Proft F, Geerlings P (2005). J Chem Phys 123:154104
Chamorro E, De Proft F, Geerlings P (2005). J Chem Phys 123:084104
Vargas R, Cedillo A, Garza J, Galvan M (2002) In: Sen KD, (ed) Reviews in modern quantum chemistry: a celebration of the contributions of Robert G. Parr. World Scientific, River Edge
Garza J, Vargas R, Cedillo A, Galvan M, Chattaraj PK (2006). Theor Chem Acc 115:257-265
Melin J, Ayers PW, Ortiz JV (2005). J Chem Sci 117:387
Day OW, Smith DW, Morrison RC (1975). J Chem Phys 62:115
Smith DW, Day OW (1975). J Chem Phys 62:113
Morrell MM, Parr RG, Levy M (1975). J Chem Phys 62:549
Ellenbogen JC, Day OW, Smith DW, Morrison RC (1977). J Chem Phys 66:4795
Matos JMO, Day OW (1987). Int J Quantum Chem 31:871
Katriel J, Davidson ER (1980). Proc Natl Acad Sci USA 77:4403
Morrison RC, Liu GH (1992). J Comp Chem 13:1004
Cioslowski J, Piskorz P, Liu GH (1997). J Chem Phys 107:6804
Morrison RC (1992). J Chem Phys 96:3718
Morrison RC (1993). J Chem Phys 99:6221
Pernal K, Cioslowski J (2001). J Chem Phys 114:4359
Levy M, Parr RG (1976). J Chem Phys 64:2707
Levy M, Perdew JP, Sahni V (1984). Phys Rev A 30:2745
Olsen J, Sundholm D (1998). Chem Phys Lett 288:282
Morrison RC, Ayers PW (1995). J Chem Phys 103:6556
Morrison RC (1994). Int J Quantum Chem 49:649
Kubo R (1962). J Phys Soc Japan 17:1100
Ayers PW, Morrison RC, Roy RK (2002). J Chem Phys 116:8731
McWeeny R (1989). Methods of molecular quantum mechanics. Academic, London
Ortiz JV (1999). Advances in quantum chemistry 35:33
Nichols JA, Yeager DL, Jorgensen P (1984). J Chem Phys 80:293
Golab JT, Yeager DL (1987). J Chem Phys 87:2925
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Ayers, P.W., Melin, J. Computing the Fukui function from ab initio quantum chemistry: approaches based on the extended Koopmans’ theorem. Theor Chem Acc 117, 371–381 (2007). https://doi.org/10.1007/s00214-006-0165-6
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DOI: https://doi.org/10.1007/s00214-006-0165-6