Abstract
The concept of electronegativity (EN), which was proposed by Pauling in 1932, is closely related to such properties of molecules as the polarizability, hardness (softness) and charge distribution, and is an important theoretical basis for judging the properties of substances. With the development of new materials and the increase of interdisciplinary cooperation, EN has been a basic atomic parameter which is widely used in the fields of chemistry, physics and materials science. The development of EN has involved three stages, atomic EN, ionic EN and bond EN. The ionic EN, which is the EN values of elements in different valence states by including the chemical environment of atoms, accurately describes various physical and chemical properties of ions and compounds. The bond EN is a bridge linking atomic EN and the properties of materials, which helps us to establish the quantitative correlation between macroscopic properties and microscopic electronic structures of materials. The concepts of ionic EN and bond EN broaden the scope of EN theory, and play important roles in the design of novel materials. This paper presents a detailed introduction of a new development of EN and its applications in materials research.
Similar content being viewed by others
References
Pauling L. The Nature of the Chemical Bond. 3rd ed. New York: Cornell University Press, 1960
Wahl U, Rita E, Correia J G, et al. Direct evidence for As as a Zn-site impurity in ZnO. Phys Rev Lett, 2005, 95(21): 215503
Zhang L, Wang E, Xue Q, et al. Generalized electron counting in determination of metal-induced reconstruction of compound semiconductor surfaces. Phys Rev Lett, 2006, 97(12): 126103
Asokamani R, Manjula R. Correlation between electronegativity and superconductivity. Phys Rev B, 1989, 39(7): 4217–4221
Hur S G, Kim T W, Hwang S, et al. Synthesis of new visible light active photocatalysts of Ba(In1/3Pb1/3M’1/3)O3 (M’ = Nb, Ta): A band gap engineering strategy based on electronegativity of a metal component. J Phys Chem B 2005, 109(31): 15001–15007
Jiang J S, Du H L, Zhang W Y. Electronegativity, atomic pseudoradii and rare earth permanent magnet materials. J Chin Rare Earth Soc, 2003, 21(3): 287–290
Lebouteiller A, Courtine P J. Improvement of a bulk optical basicity table for oxidic systems. Solid State Chem, 1998, 137(1): 94–103
Mulliken R S. A new electroaffinity scale: together with data on valence states and on valence ionization potentials and electron affinities. J Chem Phys, 1934, 2(11): 782–793
Pauling L. The origin and nature of the electronegativity scale. J Chem Educ, 1988, 65(4): 375
Allred A L, Rochow E G. A scale of electronegativity based on electrostatic force. J Inorg Nucl Chem, 1958, 5(4): 264–268
Sanderson R T. An interpretation of bond lengths and a classification of bonds. Science, 1951, 114(2973): 670–672
Allen L C. Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms. J Am Chem Soc, 1989, 111(25): 9003–9014
Phillips J C. Dielectric definition of electronegativity. Phys Rev Lett, 1968, 20(11): 550–553
Chen N Y, Chang H K. On the relationship between electronegativity and some parameters of atomic structure. Acta Chimica Sinica, 1975, 33(2): 101–112
Yuan H J. Studies on electronegativity. I. The electronegativity of atoms. Acta Chimica Sinica, 1964, 30(3): 341–347
Luo Y R, Benson S W. The covalent potential: a simple and useful measure of the valence-state electronegativity for correlating molecular energetics. Acc Chem Res, 1992, 25(8): 375–381
Iczkowski R P, Margrave J L. Electronegativity. J Am Chem Soc, 1961, 83(17): 3547
Parr R G, Donnelly R A, Levy M, et al. Electronegativity: The density functional viewpoint. J Chem Phys, 1978, 68(8): 3801–3807
Politzer P, Weinstein H. Some relations between electronic distribution and electronegativity. J Chem Phys, 1979, 71(11): 4218–4220
Sproul G. Electronegativity and bond type. 2. Evaluation of electronegativity scales. J Phys Chem, 1994, 98 (27): 6699–6703
Pearson R G. Electronegativity scales. Acc Chem Res, 1990, 23(1): 1–2
Allred A L, Rochow E G. Electronegativity values from thermochemical data. J Inorg Nucl Chem, 1961, 17 (3–4): 215–221
Frost R L, Erickson K L, Weier M L, et al. Use of infrared spectroscopy for the determination of electronegativity of rare earth elements. Appl Spectrosc, 2004, 58(7): 811–815
Leyssens T, Geerlings P, Peeters D. A group electronegativity equalization scheme including external potential effects. J Phys Chem A, 2006, 110(28): 8872–8879
Sanderson R T. Electronegativities in inorganic chemistry. J Chem Educ, 1954, 31(1): 2–7
Zhang Y H. Electronegativities of elements in valence states and their applications. Inorg Chem, 1982, 21(11): 3886–3893
Sanderson R T. Electronegativity and bonding of transitional elements. Inorg Chem, 1986, 25(19): 3518–3522
Li K, Xue D. Estimation of electronegativity values of elements in different valence states. J Phys Chem A, 2006, 110(39): 11332–11337
Asthagiri D, Pratt L R, Paulaitis M E, et al. Hydration structure and free energy of biomolecularly specific aqueous dications, including Zn2+ and first transition row metals. J Am Chem Soc, 2004, 126(4): 1285–1289
Su Q. Chemistry of Rare Earths. Zhengzhou: Henan Science and Technology Press, 1993
Li K, Xue D. A new set of electronegativity scale for trivalent lanthanides. Phys Stat Sol B, 2007, 244 (6): 1982–1987
Brown I D, Skowron A. Electronegativity and Lewis acid strength. J Am Chem Soc, 1990, 112(9): 3401–3403
Luo Y R, Benson S W. A new electronegativity scale. 12. Intrinsic Lewis acid strength for main-group elements. Inorg Chem, 1991, 30(7): 1677–1680
Tsuruta H, Yamaguchi K, Imamoto T, et al. Tandem mass spectrometric analysis of rare earth(III) complexes: evaluation of the relative strength of their Lewis acidity. Tetrahedron, 2003, 59(52): 10419–10438
Hinze J, Whitehead M A, Jaffe H H. Electronegativity. II. Bond and orbital electronegativities. J Am Chem Soc, 1963, 85(2): 148–154
Ghosh S K. Toward a semiempirical density functional theory of chemical binding. Theor Chim Acta, 1987, 72(5–6): 379–391
Cui B Q, Zhao D X, Yang Z Z. Prediction of reactive site in superoxide dismutase in terms of atom-bond electronegativity equalization method. Acta Chimica Sinica, 2007, 65(23): 2687–2692
Li K, Wang X, Xue D. Electronegativities of elements in covalent crystals. J Phys Chem A, 2008, 112(34): 7894–7897
Li K, Wang X, Zhang F, et al. Electronegativity identification of novel superhard materials. Phys Rev Lett, 2008, 100(23): 235504
Jansen M, Letschert H P. Inorganic yellow-red pigments without toxic metals. Nature, 2000, 404(6781): 980–982
Asahi R, Morikawa T, Ohwaki T, et al. Visible-light photocatalysis in nitrogen-doped titanium oxides. Science, 2001, 293(5528): 269–271
Author information
Authors and Affiliations
Corresponding author
Additional information
Supported by the Program for New Century Excellent Talents in University (Grant No. NCET-05-0278) and Foundation for the Author of National Excellent Doctoral Dissertation of China (Grant No. 200322)
About this article
Cite this article
Li, K., Xue, D. New development of concept of electronegativity. Chin. Sci. Bull. 54, 328–334 (2009). https://doi.org/10.1007/s11434-008-0578-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11434-008-0578-9