Journal of Molecular Modeling

, 24:231 | Cite as

Chemical descriptors for describing physico-chemical properties with applications to geosciences

  • Jean-Louis VigneresseEmail author
  • Laurent Truche
Original Paper
Part of the following topical collections:
  1. International Conference on Systems and Processes in Physics, Chemistry and Biology (ICSPPCB-2018) in honor of Professor Pratim K. Chattaraj on his sixtieth birthday


Chemical descriptors using DFT concepts characterize elements reactivity. Such descriptors, namely hardness and electrophilicity, are components of the derivative of the chemical potential. Their values form a new coordinates system, on which a third parameter can be mapped. The simplest mapping is the chemical potential itself, but other mapping may involve totally different chemical or physical parameters. Examples use rock analyses generated within the continental or oceanic crust of the Earth. They are usually described in an 11D system of major oxides. The new system of coordinates reduces the description to a more easily tractable 2D diagram. It also represents a base for plotting other chemical information, such as the normative component composition or a combination of them. Physically, other properties, such as the polymerization state or viscosity values, can be used to produce a 3D topography. Other topographic surfaces similar to the chemical potential of elements can be mapped, allowing quantification of partition coefficient values when elements fractionate in both liquid or viscous states. The reduction of an 11D diagram to a 2D one is suggested in other scientific descriptions of complex combinations.

Graphical abstract

[ω-η] diagrams showing the chemical potential and the different continental and oceanic rock typesthen ading some chemical (Aluminium Saturation Index) parameter.


DFT Chemico–physical descriptors Rocks and minerals evolution Elements partitioning 



The paper came out after a stay at the Department of Chemistry, IIT Kharagpur, India, with granting by the CTS (Center for Theoretical Studies). It allowed fruitful introduction to DFT concepts and collaboration with Pratim K. Chattaraj and his students. Discussions with Christophe Morell (Université de Lyon1) encouraged me to formulate what is now this paper. Constructive reviews with comments are also warmly acknowledged.

Compliance with ethical standards

Confict of interest

There is no conflict of interest.


  1. 1.
    Pearson RG (1963) Hard and soft acids and bases. J Am Chem Soc 85:3533–3539CrossRefGoogle Scholar
  2. 2.
    Pearson RG (1988) Absolute electronegativity and hardness: application to inorganic chemistry. Inorg Chem 27:734–740CrossRefGoogle Scholar
  3. 3.
    Chattaraj PK, Lee H, Parr RG (1991) HSAB principles. J Am Chem Soc 113:1855–1856CrossRefGoogle Scholar
  4. 4.
    Pearson RG (2009) The hardness of closed systems. In: Chattaraj PK (ed) Chemical reactivity theory: a density functional view. CRC, Boca Raton, pp 155–163Google Scholar
  5. 5.
    Parr RG, Yang W (1984) Density functional approach to the frontier-electron theory of chemical reactivity. J Am Chem Soc 106:4049–4050CrossRefGoogle Scholar
  6. 6.
    Chermette H (1999) Chemical reactivity indexes in density functional theory. J Comput Chem 20:129–154CrossRefGoogle Scholar
  7. 7.
    Geerlings P, De Proft F, Langenaeker W (2003) Conceptual density functional theory. Chem Rev 103:1793–1873CrossRefPubMedPubMedCentralGoogle Scholar
  8. 8.
    Chattaraj PK, Maiti B (2004) Regioselectivity in the chemical reactions between molecules and protons: a quantum fluid density functional study. J Phys Chem A 10:658–664CrossRefGoogle Scholar
  9. 9.
    Vigneresse JL, Duley S, Chattaraj PK (2011) Describing the chemical character of a magma. Chem Geol 287:102–113CrossRefGoogle Scholar
  10. 10.
    Vigneresse JL (2012) Chemical reactivity parameters (HSAB) applied to magma evolution and ore formation. Lithos 153:154–164CrossRefGoogle Scholar
  11. 11.
    McBirney AR (1993) Igneous petrology. Jones and Bartlett, Boston, p 572Google Scholar
  12. 12.
    Pearce JA, Harris NBW, Tindle AW (1984) Trace element discrimination diagrams for the tectonic interpretation of granitic rocks. J Petrol 25:956–983CrossRefGoogle Scholar
  13. 13.
    Chayes F (1971) Ratio correlation a manual for students of petrology and geochemistry. Univ Chicago Press, Chicago, p 99Google Scholar
  14. 14.
    Pauling L (1932) The nature of the chemical bonds. IV The energy of single bonds and the relative electronegativity of atoms. J Am Chem Soc 54:3570–3582CrossRefGoogle Scholar
  15. 15.
    Chattaraj PK, Giri S, Duley S (2012) Update 2 of: Electrophilicity index. Chem Rev 111:PR43–PR75Google Scholar
  16. 16.
    Ghanty TK, Gosh SK (1996) A density functional approach to hardness, polarizability, and valency of molecules in chemical reactions. J Phys Chem 100:12295–12298CrossRefGoogle Scholar
  17. 17.
    Morell C, Grand A, Toro-Labbé A (2005) New dual descriptor for chemical reactivity. J PhysChem A109:205–212Google Scholar
  18. 18.
    Mortier WJ, Ghosh SK, Shankar S (1986) Electronegativity-equalization method for the calculation of atomic charges in molecules. J Am Chem Soc 108:4315–4320CrossRefGoogle Scholar
  19. 19.
    Parr RG, Chattaraj PK (1991) Principle of maximum hardness. J Am Chem Soc 113:1854CrossRefGoogle Scholar
  20. 20.
    Chattaraj PK (1996) The maximum hardness principle: an overview. Proc Indian Nat Sci Acad A62:513–531Google Scholar
  21. 21.
    Pan S, Sola M, Chattaraj PK (2013) On the validity of the maximum hardness principle and the minimum electrophilicity principle during chemical reactions. J Phys Chem A 117:1843–1852CrossRefPubMedGoogle Scholar
  22. 22.
    Noorizadeh S, Shakerzadeh E (2008) A new scale of electronegativity based on electrophilicity index. J Phys Chem A 112:3486–3491CrossRefPubMedGoogle Scholar
  23. 23.
    Morel C, Labet V, Grand A, Chermette H (2009) Minimum electrophilicity principle: an analysis based upon the variation of both chemical potential and absolute hardness. Phys Chem Chem Phys. 14:3417–3423CrossRefGoogle Scholar
  24. 24.
    Torrent-Sucarrat M, Luis JM, Duran M, Sola M (2001) On the validity of the maximum hardness and minimum polarizability principles for nontotally symmetric vibrations. J Am Chem Soc 123:7951–7952CrossRefPubMedGoogle Scholar
  25. 25.
    Wright S (1932) The roles of mutation, inbreeding, crossbreeding and selection in evolution proc. Sixth Ann Congr Genetics 1:356–366Google Scholar
  26. 26.
    Kauffman SA (1995) At home in the universe: the search for Laws of self-organization and complexity. Oxford University Press, New York 321 pp Google Scholar
  27. 27.
    Duley S, Vigneresse JL, Chattaraj PK (2012) Fitness landscapes in natural rocks system evolution: a conceptual DFT treatment. J Chem Sci 124:29–34CrossRefGoogle Scholar
  28. 28.
    Das R, Vigneresse JL, Chattaraj PK (2014) Redox and Lewis acid–base activities through an electronegativity-hardness landscape diagram. J Mol Model 19:4857–4864CrossRefGoogle Scholar
  29. 29.
    Mysen BO, Richet P (2005) Silicate glasses and melts. Elsevier, Amsterdam, p 544Google Scholar
  30. 30.
  31. 31.
    Rollinson HR (1993) Using geochemical data: evaluation, presentation, interpretation. Longman Scientific and Technical, Harlow, p 352Google Scholar
  32. 32.
    Stacey FD, Banerjee SK (1974) The physical principles of rock magnetism. Elsevier, Amsterdam, p 204Google Scholar
  33. 33.
    Jugo PJ, Luth R, Richards J (2005) Experimental study of the sulfur content in basaltic melts saturated with immiscible sulfide or sulfate liquids at 1300 °C and 10 GPa. J Petrol 46:783–798CrossRefGoogle Scholar
  34. 34.
    Jégo S, Dasgupta R (2014) The fate of sulfur during fluid-present melting of subducting basaltic crust at variable oxygen fugacity. J Petrol 55:1019–1050CrossRefGoogle Scholar
  35. 35.
    Ishihara S (2004) The redox state of granitoids relative to tectonic setting and earth history: the magnetite–ilmenite series 30 years later. Trans R Soc Edinb Earth Sc 95:23–33CrossRefGoogle Scholar
  36. 36.
    Ottonello G, Moretti R, Marini L, Vetuschi Zuccolini M (2001) Oxidation state of iron in silicate glasses and melts: a thermochemical model. Chem Geol 17:157–179CrossRefGoogle Scholar
  37. 37.
    Candela PA (1989) Felsic magmas, volatiles, and metallogenesis. In: Whitney JA, Naldrett AJ (eds) Ore deposition associated with magmas. Rev Econ Geol 4:223–233Google Scholar
  38. 38.
    Blundy J, Wood B (2003) Partitioning of trace elements between crystals and melts. Earth Planet Sci Lett 210:383–397CrossRefGoogle Scholar
  39. 39.
    Zhang Y, Ni H, Chen Y (2010) Diffusion data in silicate melts. Rev Min Geochem 72:311–408CrossRefGoogle Scholar
  40. 40.
    Bodnar RJ (1995) Fluid-inclusion evidence for a magmatic source of metals in porphyry copper deposits. In: Thompson JFH (ed) Magmas, fluids, and ore deposits. Mineral Ass. Canada Short Course Series 23:139–52Google Scholar
  41. 41.
    Frezzotti ML (2001) Silicate-melt inclusions in magmatic rocks: applications to petrology. Lithos 55:273–299CrossRefGoogle Scholar
  42. 42.
    Kamenetsky VS, Kamenestsky MB (2010) Magmatic fluids immiscible with silicate melts: examples from inclusions in phenocrysts and glasses, and implications for magma evolution and metal transport. Geofluids 10:293–311Google Scholar
  43. 43.
    Li Y, Audétat A (2012) Partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulphide phases and hydrous basanite melt at upper mantle conditions. Geochim Cosmochim Acta 75:1673–1692Google Scholar
  44. 44.
    Zajacz Z, Candela PA, Piccoli PC, Sanchez-Valle C, Wälle M (2013) Solubility and partitioning behavior of Au, Cu, Ag and reduced S in magmas. Geochim Cosmochim Acta 112:288–304CrossRefGoogle Scholar
  45. 45.
    Ghosh DC, Chakraborty T (2009) Gordy’s electrostatic scale of electronegativity revisited. J Mol Struct THEOCHEM 906:87–93CrossRefGoogle Scholar
  46. 46.
    Atlan H (1989) Automata networks in immunology : their utility and their underdetermination. Bull Math Biol 54:247–253CrossRefGoogle Scholar
  47. 47.
    Berg JM (2015) Biochemistry, W.H. Freeman, 1232 pp.Google Scholar
  48. 48.
    Atlan H (2018) Cours de Philosophie Biologiste et Cognitive. Odile Jacob (ed.), Paris, p 637Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Université de LorraineVandoeuvre CédexFrance
  2. 2.ISTerreUniversité de Grenoble-AlpesSaint-Martin-d’HèresFrance

Personalised recommendations