Abstract
This chapter is an exploration of the applicability of quantum chemistry to central aspects of chemical knowledge like the concept of chemical bond and its material background. Lewis’s electronic theory, precursor of modern quantum chemistry, is discussed, and the works of Linus Pauling and Hans Primas are examined from a conceptual viewpoint. Finally, the general limitation of the quantum approach with respect to the chemistry of substances is emphasized.
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Notes
- 1.
This trichotomy is represented in modern textbooks, for example in the famous work by Holleman and Wiberg (1964), in which the ideal types mentioned are referred to as first-order bonds.
- 2.
Within the scope of his criticism of Kripke’s and Putnam’s theories of meaning, Hacking briefly outlines the early history of the electron and states: “No one at present doubts that the electron is a natural kind of fundamental importance” (Hacking, 1983: 84). For the sake of neutrality, note that electrons in a culturalist perspective are theoretical entities or “constructs” (Psarros, 1999: 306) and their “discovery” is thus essentially an invention (Hanekamp, 1997: 227).
- 3.
According to Laidler (1993: 206), Faraday himself came close to a similar interpretation, although his notion of electricity as a fluid prevented him from coming to a strict atomistic and corpuscular interpretation.
- 4.
Gilbert Lewis also failed to note the Irishman as late as 1923 when he wrote: “It was Helmholtz in his celebrated Faraday lecture of 1881 who first pointed out this deduction of the atom of electricity, or as it is now called, the electron.” (Lewis, 1923: 21).
- 5.
An early indication of this is the statement by Ida Freund (1904: 540): “Not more than a beginning has been made as yet; but whilst formerly it had not even been possible to say what class of conceptions were likely to supply the building material for the adequate hypothesis and theory of valency that is required, it now seems probable that these conceptions will be the indivisible ‘electron,’ to which the ions owe their electrical charges and the lines of force connecting the electrons.”
- 6.
- 7.
He received the Nobel Prize in 1919 for the discovery of the optical Doppler effect in canal rays and the splitting of spectral lines in electric fields. It bears mention here that Stark later became a fervent supporter of National Socialism and the so-called “German physics” yet after the war went practically unpunished, see Mehrtens and Richter (1980) and Hoffmann (2005).
- 8.
With respect to the discussion of the existence of stable atoms, Heisenberg speaks of binding energies and chemical forces; for him the binding of even one electron in an isolated atom represents a “chemical” bond (Heisenberg, 1989: 89).
- 9.
- 10.
A particle’s intrinsic rotational impulse is referred to as spin in quantum mechanics. It can assume two values for one energy level and is thus a half-integer lacking a classical correlate and cannot really be depicted. Only with the assumption of spin can all phenomena occurring in the line spectra be fully accounted for. The formation of an electron pair in a covalent chemical bond is not comprehensible in a classic sense because particles of the same charge should repel rather than attract each other. In the statement quoted at the beginning, Coulson projects the current state of knowledge a bit too far back.
- 11.
- 12.
Cf. the fresh appreciation of Abegg in Scerri (2016: 63–78).
- 13.
The first paper on this topic was the programmatic study by Abegg and Bodländer (1899).
- 14.
Something similar may be found in the short physiologically motivated work by Georg Buchner. The glossary entry under electroaffinity reads as follows: “The elementary atoms combine not only with other elementary atoms but also have the ability to bind electricity atoms (electrons) (electroaffinity). According to the unitary view of electricity, we refer to the elementary atoms connected with electrons as negative ions and the elementary atoms that have given off electrons as positive ions. The binding force for electrons increases with the electronegative character of the elementary atoms.” (Buchner, 1912: 136; my emphasis). Note that Buchner does not mention Abegg.
- 15.
At this point I will skip over the classic topic of the preservation of elements when forming and separating composite substances and its semantic peculiarities.
- 16.
Lewis , in the same place, calls the approach “the theory of the cubical atom” and dates its inception to the preparation for an introductory lecture of 28 March 1902. He notes that it was not the priorities that were important to him but the common ground with similar theoretical attempts (aside from Abegg, whom he mentions explicitly, certainly the one by Kossel as well), whereby the fact that “all possess some characteristics of fundamental reality” would contribute to their probability. He does not have a realistic microstructural interpretation in mind.
- 17.
Langmuir’s introductory statement in this work is telling: “The problem of the structure of atoms has been attacked mainly by physicists who have given little consideration to the chemical properties which must ultimately be explained by a theory of atomic structure. The vast store of knowledge of chemical properties and relationships, such as is summarized by the Periodic Table, should serve as a better foundation for a theory of atomic structure than the relatively meager experimental data along purely physical lines. ” (Langmuir, 1919: 868). The American industrial chemist Langmuir (who received his doctorate in 1909 in Göttingen) received the Nobel Prize in 1932 for work in the field of surface chemistry.
- 18.
Cf. the detailed discussion of this episode from the perspective of the philosophy of chemistry in van Brakel (2000: 27–34). The author comes to the following evaluation (ibid.: 34): “The debates about the theory of resonance show that nationalistic concerns were of much greater importance than the dogma’s of dialectical materialism. The concerns of the debates and power machinations in Moscow promoting Buterlov had no followers in the GDR –though it is no doubt correct that Butlerov’s importance had been suppressed in German and English text books that gave reviews of the history of organic chemistry.”
- 19.
- 20.
Cf. Staab (1959: 642–650)
- 21.
Jaap van Brakel (2012) refers to this point.
- 22.
Psarros (1999: 169) says of the oxidation number: “It specifies which valence level the atoms of a given nonmetal assume when they are combined with atoms of other elements.” First, this characterization is incomplete because it mentions only nonmetals and, second, it is unclear because the oxidation number has nothing to do with valence (itself a concept requiring clarification) but with the ratio of the sorts of atoms involved to the electrons available for binding (valence electrons), cf. Riedel (2004: 128).
- 23.
With this deduction it is assumed (from experience) that the basic arrangement of the sulfate ion is such that the sulfur atom is in the center and the oxygen atoms arrange themselves around it. Compounds with oxygen atoms can be excluded here.
- 24.
Naturally, the assumption that atoms and electrons exist itself presupposes that the samples of substances can be divided or quantized at the submicroscopic level. Yet quantum mechanics was not yet used here.
- 25.
There are arguments in favor of continuing to classify the octet rule as not merely heuristic but to take it seriously even from a theoretical standpoint. See Weidenbruch (1994: 20): “Lewis’s octet rule has lost none of its validity since it was first formulated over 90 years ago. It applies to compounds of the main group of elements with the correct number of electrons, which include nearly all organic compounds, as well as to compounds with excess electrons in which the supernumerary electrons can be accommodated in nonbinding orbitals of the substitutes.”
- 26.
In this “wave equation” E and V are, respectively, the kinetic and potential energy of an electron in an electric field (between nucleus and electron), m is the mass of the electron, ħ in the Planck constant h/2π, and ∇ (the “Laplace operator”) has the form ∂/∂x2 + ∂/∂y2 + ∂/∂z2 for the usual three-dimensional case. Where the mass of the electron is regarded as unchanging, we refer to the time-independent or nonrelativistic Schrödinger equation .
- 27.
- 28.
The wave number of the “Balmer series” is expressed today as \( \tilde{\nu}={R}_{\infty}\left(1/{2}^2-1/{n}^2\right) \), with the Rydberg constant R∞ and n = 3, 4, …
- 29.
I refer to the modern nuclear and quantum physicists in this manner because the Schrödinger equation at its core has to do with potential and kinetic energy.
- 30.
In Die Natur der Chemischen Bindung, Pauling states: “Before 1927 there was no satisfactory theory for the covalent bond. The chemists had postulated the existence of a valence bond between the atoms, a notion that was corroborated by experience, but all efforts at gaining insight into the nature of the bond had remained largely unsuccessful. Lewis, who associated two electrons with one bond, took a step forward in doing so, yet one can hardly speak of the development of a theory. The decisive questions as to the nature of the interaction and the cause of the binding energy remain unanswered.” (Pauling, 1962: 21).
- 31.
Cf. Ladik, 1973: 203–212.
- 32.
Regarding “electron exchange” Heitler states: “The electron exchange is […] primarily a typical quantum mechanical effect and all attempts to find a ‘classic analogy’ must fail […]. The cause of the exchange effect is the very fact that electrons are indistinguishable and therefore an exchange of electrons is principally unobservable.” (Heitler, 1961: 99–100).
- 33.
Fig. 19 from Ladik (1973: 216). The x axis shows Bohr radius units (0,5285 A); the y axis shows the (potential) energy in electron volts. ES shows the ground state; EA shows the first excited state. Dashed lines show measured values; solid lines show calculated values. Figures with identical content are also found in other introductions, including Heitler and London (1927: 462) and Heitler (1961: 98).
- 34.
The same scheme is used for the discussion of a possible helium molecule He2, whereby the total of four electrons now, in addition to fully occupying the binding state, would also fully occupy the antibinding state, which explains the nonexistence of this particle (or a substance consisting of it).
- 35.
Regarding the over hundred-year-old history of electronegativity, see the works of Bill Jensen (1996, 2003, 2012). Ruthenberg and Martínez González (2017) examine this topic from the perspective of the philosophy of chemistry. Many modern representations follow Pauling and provide an unnecessarily abbreviated definition of electronegativity, as is the case in Riedel (2004: 119): “A measure of the capacity of an atom to draw the binding electron pair toward itself in an atomic bond is electronegativity.”
- 36.
Fig. 3–8 from Pauling (1962: 95).
- 37.
Accordingly, Preuss (1960: 241) discusses Pauling’s approach as a “semi-empirical method.”
- 38.
There are attempts to calculate electronegativities from spectrometric data, from dipole moments, and from electron affinities and ionization energies (cf. Ruthenberg & Martínez González, 2017).
- 39.
With respect to this publication, an introduction to quantum chemistry, I regard Primas as the senior author and especially as the source of the more philosophical comments, which here are particularly clear and productive. Other pertinent references include Primas (1983, 1985a, b, 1992). Cf. the article by Amann and Gans (1989), authors close to Primas in terms of content.
- 40.
- 41.
I have borrowed this formulation, which describes the situation very well, from Preuss (1960: 241). It should be noted that such representations and similar ones occasionally convey (or possibly are intended to convey) the impression that the words “quantum mechanical” impart the content a particularly high degree of scientific reliability and significance. At the same time the relationship between empiricism and theory is often nearly turned upside down when it is repeatedly emphasized that quantum mechanics is among the physical theories best confirmed by experimental findings, whereas its origin from spectroscopic experience is practically ignored.
- 42.
See the extraordinarily comprehensive presentation, not exclusively referring to French (philosophy of) chemistry, by Bernadette Bensaude-Vincent (2009).
- 43.
The textbook in question by the Princeton chemists Glasstone et al. (1941) contains the original graphic of the potential surface representation on page 96. Primas and Müller-Herold also reproduce this figure (1990: 202) and briefly discuss “adiabatic reactions” although this is not actually a genuinely quantum chemical topic. In their summary they state (1990: 205): “Often even a contemplation of the plausibility of the structure of the transitional complexes allows interesting qualitative statements to be made about the possible course of chemical reactions.” Hinne Hettema (2012) discusses the case study of the “absolute reaction rate theory” from the standpoint of the philosophy of chemistry. The author is receptive to reductionism in the sense of a path to a unified natural science and regards the theory of the transitional state as a typical example of this attitude.
- 44.
Other authors also come to a similar conclusion. Paul Bogaard for example writes in a brief but very informative article about the influence of Gilbert Lewis on Linus Pauling and Charles Coulson about the latter’s opinion (2003: 308): “Molecular structure –and the search for directionality of bonding that could produce it– is motivated neither by the mathematical formalisms of quantum theory nor by the physics which underlies quantum mechanics, but by experience with chemical substances.”
- 45.
By observable is meant somehow physically tangible and therefore measurable values.
- 46.
They note that the Bohm variant of quantum mechanics has better chances of being compatible with the QTAIM but they do not expand on this idea (ibid.: 135).
- 47.
I see this as further support for my claim that energetics and kinetics are fundamentally different chemical concepts.
- 48.
The examples listed come from Primas and Müller-Herold (1990: 125 and 197).
- 49.
Here I have borrowed part of the title of the book Macroscopic Metaphysics – Middle-Sized Objects and Longish Processes by Paul Needham, which is in fact a work in the philosophy of chemistry (Needham, 2017).
- 50.
In the textbook Philosophie und Naturwissenschaften by a group of East German authors, we read: “The achievement of quantum theory as applied to chemical problems consists not only in having provided a more adequate theory of the chemical bond but also in the realization that the laws of the macro level cannot be directly applied to the micro level.” (Author collective, 1988: 189). I agree with this, although I note that the reverse statement is also true; it is equally impossible to apply the laws of the micro level to the macro level.
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Acknowledgments
I thank Olimpia Lombardi and Juan Camilo Martínez González for the opportunity to contribute to this volume, for the help with the manuscript, and for all the discussions during the last decade. I also thank an anonymous referee for comments which helped to improve the article. The manuscript was written in German by the author and translated into English by John Grossman. I thank him as well.
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Ruthenberg, K. (2022). How Chemical Is Quantum Chemistry?. In: Lombardi, O., Martínez González, J.C., Fortin, S. (eds) Philosophical Perspectives in Quantum Chemistry. Synthese Library, vol 461. Springer, Cham. https://doi.org/10.1007/978-3-030-98373-4_2
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