Abstract
Fluctuation formulas for the external potential v(r) are introduced in a modified Legendre-transformed representation of the density functional theory of electronic structure (isomorphic ensemble). A new (nuclear/geometric) reactivity index h(r), having the same status as the electronic Fukui function in the canonical ensemble, is thereby identified, h(r)=(1/N)[δμ/δσ(r)]N,T=(1/kT) [〈μ⋅v(r)〉−〈μ〉〈v(r)〉], where μ is the electronic chemical potential, σ is the shape factor of the electron density distribution, N is the number of electrons, 〈...〉 denotes the ensemble average of a quantity, and 〈v(r)〉 is the ensemble averaged external potential. This new local quantity is shown to be an inverse of the local softness, and to provide a useful definition of a local hardness.
References
34
Referenced
88
10.1103/PhysRev.136.B864/ Phys. Rev. B (1964){'key': '2024020615271509300_r2', 'first-page': '4049', 'volume': '104', 'year': '1984', 'journal-title': 'J. Am. Chem. Soc.'}/ J. Am. Chem. Soc. (1984)10.1073/pnas.82.20.6723/ Proc. Natl. Acad. Sci. USA (1985)10.1063/1.454034/ J. Chem. Phys. (1988)10.1063/1.449846/ J. Chem. Phys. (1985)10.1021/ja00310a011/ J. Am. Chem. Soc. (1985)10.1016/0009-2614(90)87220-L/ Chem. Phys. Lett. (1990)10.1063/1.468026/ J. Chem. Phys. (1994)10.1021/j100024a020/ J. Phys. Chem. (1995){'key': '2024020615271509300_r8'}10.1073/pnas.82.20.6723/ Proc. Natl. Acad. Sci. USA (1985)10.1002/ijch.199100045/ Isr. J. Chem. (1991)10.1007/BFb0036797/ Struct. Bond. Chem. Hardness (1993)10.1021/ja00005a072/ J. Am. Chem. Soc. (1991)10.1021/ja00005a073/ J. Am. Chem. Soc. (1991){'key': '2024020615271509300_r14', 'first-page': '1441', 'volume': '137', 'year': '1965', 'journal-title': 'Phys. Rev. A'}/ Phys. Rev. A (1965)10.1063/1.443620/ J. Chem. Phys. (1982){'key': '2024020615271509300_r16'}10.1073/pnas.82.8.2207/ Proc. Natl. Acad. Sci. USA (1985){'key': '2024020615271509300_r18'}{'key': '2024020615271509300_r19'}10.1021/j100238a023/ J. Phys. Chem. (1983){'key': '2024020615271509300_r21', 'first-page': '231', 'volume': '28', 'year': '1994', 'journal-title': 'Int. J. Quantum Chem. Chem. Symp.'}/ Int. J. Quantum Chem. Chem. Symp. (1994)10.1021/ja00364a005/ J. Am. Chem. Soc. (1983){'key': '2024020615271509300_r23'}{'key': '2024020615271509300_r24'}10.1021/ja00310a011/ J. Am. Chem. Soc. (1985)10.1021/j100058a044/ J. Phys. Chem. (1994)10.1021/ja00275a013/ J. Am. Chem. Soc. (1986)10.1016/0022-3697(89)90427-7/ J. Phys. Chem. Solids (1989)10.1021/ja00018a003/ J. Am. Chem. Soc. (1991)10.1007/BFb0036804/ Struct. Bond. Chem. Hardness (1993){'key': '2024020615271509300_r31', 'first-page': '65', 'volume': '43A', 'year': '1988', 'journal-title': 'Z. Naturforsch.'}/ Z. Naturforsch. (1988)10.1007/BFb0036803/ Struct. Bonding Chem. Hardness (1993)
Dates
| Type | When |
|---|---|
| Created | 23 years ago (July 26, 2002, 8:34 a.m.) |
| Deposited | 1 year, 6 months ago (Feb. 6, 2024, 10:41 a.m.) |
| Indexed | 2 months, 3 weeks ago (May 28, 2025, 10:03 a.m.) |
| Issued | 29 years, 9 months ago (Nov. 15, 1995) |
| Published | 29 years, 9 months ago (Nov. 15, 1995) |
| Published Print | 29 years, 9 months ago (Nov. 15, 1995) |
@article{Baekelandt_1995, title={Reactivity indices and fluctuation formulas in density functional theory: Isomorphic ensembles and a new measure of local hardness}, volume={103}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.470165}, DOI={10.1063/1.470165}, number={19}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Baekelandt, Bart G. and Cedillo, Andrés and Parr, Robert G.}, year={1995}, month=nov, pages={8548–8556} }