Critique of Quantum Mechanics in Chemistry
| Scientific Paper | |
|---|---|
| Title | Critique of Quantum Mechanics in Chemistry |
| Read in full | Link to paper |
| Author(s) | Sithamalli K Balasubramanian |
| Keywords | quantum mechanics, Quantum Theory, Cold Fusion |
| Published | 2009 |
| No. of pages | 16 |
Read the full paper here
Abstract
The major failures of Quantum Mechanics are in chemistry. These had been overlooked because of the notion, attributed to P.A.M.Dirac, that QM solves ALL the problems of Chemistry and major parts of those in Physics. The difficulties in application to Chemistry are not simply a matter of complicated mathematics involved in the process. There are severe problems of elementary logic. The problem may be indicative of a deeper malaise. It may be the basic premise of QM itself that is questionable. We leave it open and limit ourselves to the deficiencies in the application of QM to Chemistry. The citations below are mostly to books. The concepts under criticism are part of the School curriculum the world over. They are not abstractions found in fringe literature; hence the importance of the Critique.
The difficulties are dealt with under the following heads:
- Chirality of molecules and molecular systems: Molecular chirality is incompatible with QM
- Aufbau model and its application to chemical systems
- Molecular systems: ad hoc approaches
- Electric Current and magnetism
- Inert Gases, superconductivity and Meissner effect
- Cold fusion
- Proton sites and nuclear structure
- Central dogma
Overview
The paper, subtitled "Unitary Model for atomic structure," is written by Sithamalli K Balasubramanian, a chemist writing from Pune, India. Its target is not the mathematics of quantum mechanics but its application in chemistry, and its method is a catalogue: eight headings, each collecting cases where — on the author's reading — the standard treatment either fails outright or is rescued only by an assumption invented for the occasion. He is explicit that the citations are to textbooks rather than to fringe sources, and that this is the point: "the concepts under criticism are part of the School curriculum the world over."
Balasubramanian's positive proposal is what he calls the Unitary Model, which is sketched rather than developed. Its two working ideas are that the number of electrons on an atom is not fixed but can "rise and subside" depending on chemical context, and that bonding sites correspond to proton sites located on the surface of the nucleus, so that atomic structure is genuinely structural rather than probabilistic. He states the conflict with orthodoxy sharply: because the tetrahedral geometry of carbon survives in every bonding context, "there is no chance for probability about the behavior of electrons. This is the fundamental conflict between our model and QM."
The eight difficulties
Chirality
The paper opens with what it regards as the strongest case. Optical isomers are separable, independently stable, and identical except in the sense in which they rotate polarised light; chiral systems are fundamental in biology, where "in entirety life molecules are based on a single chiral sense." Balasubramanian cites R. G. Woolley's 1978 paper in the Journal of the American Chemical Society as concluding that quantum mechanics does not permit chirality, and a 1984 discussion by Weininger as concluding that the theory applies to a single molecule and not to a collection, so that an isolated chiral molecule would lose its chirality. "The most fundamental phenomenon of Chemistry is not accountable on the QM."
The aufbau model
A series of cases is offered against the shell-filling picture. Carbon's 1s22s22p2 configuration is ideally divalent, and tetravalency is recovered only by hybridisation, which he calls "equating inequalities" since the 2s and 2p orbitals differ in energy and orientation. Beryllium, with closed 1s22s2 shells, should be inert but is not, the standard escape being its vacant 2p shell; argon, with a vacant 3d shell, should by the same reasoning be reactive but is not. Placing the 4s level below the vacant 3d is, on his reading, "an assumption treated as an explanation."
He then attacks the identification of atomic number with electron count. Moseley's X-ray data did not give a straight line for Z2 against frequency but did for (Z−1)2, explained before 1980 by an electron falling into the nucleus and afterwards by plotting Z against the square root of frequency. Balasubramanian calls the latter "obfuscation of an excellent experimental result," on the ground that compressing the ordinate can straighten any curve, and concludes that Moseley's work shows a correlation with the ordering of elements by mass number, leaving the identification of atomic number with nuclear charge open.
The evidential support offered for a variable electron count comes from volatile fluorides. UF6 is the heaviest binary molecule yet is a gas above 55 °C despite a nominal 86 non-bonded electrons; BF3, CF4, SiF4, GeF4 are gases; SF6, SeF6 and TeF6 are gases and dielectrics, the latter showing that "electron effects are totally and measurably absent"; phosphorus and arsenic, normally donors, form trifluorides that act as acceptor ligands and pentafluorides that are Lewis acids; nickel tetracarbonyl is a gas above 30 °C. He infers that charges "rise and subside" in an atom, a process distinct from beta decay, to which Soddy's displacement law does not apply, and which he speculates is mediated by the weak force. A final structural objection: space has three dimensions, exhausted by the p orbitals, so the shapes of higher orbitals are "mathematical constructs" with no physical realisation.
Ad hoc bonding schemes
Three cases are offered as evidence that each new bonding phenomenon brings a new assumption — "Procrustean methods," a shifting of goal posts. Zeise's salt requires the σ-donation/π-back-donation bond, which he argues postulates an energy gain over the cycle A→B→A and so "should make perpetual motion close to realization." Propellane (given as C5H6) is stable below 100 °C yet its axial bond points the wrong way for tetrahedral geometry and must be called an "inverted bond"; here "there is no room even for ad hoc assumption. The theory breaks down totally." He links this to bimolecular nucleophilic substitution: if there can be no electron density along the inverted direction, backside substitution should not occur, yet it is ubiquitous in carbon chemistry and absent for other elements. Boron supplies the third case, with the two-electron three-centre bond of diborane and the icosahedra of crystalline boron.
Two further phenomena are attributed to chirality at the atomic level rather than to molecular orbital theory: the paramagnetism of O2, which he says requires a "chiral plane" across which moments do not cancel and which he also invokes for the antiferromagnetism of FeO and MnO; and the linear dichroism of crystalline anthracene, anisotropic absorption in a molecule that looks symmetrical.
Current, magnetism, cold states and the nucleus
Section 4 argues that electric current cannot be carried by a massive particle: the speed is high and comparable to light, independent of voltage, so a 12 V telephone circuit and a high-voltage line propagate alike. He proposes instead a helical charge-carrying vector field, the helical form inferred from the shallow penetration of current below a conductor's surface and supported by the helical arrangement of aromatic rings in carbon nanotubes; the two halves of an alternating current are then two chiralities. Magnetism is a single charge helix riding "piggy back" on low-frequency radiation, giving four combinations, AB-C, AB-D, BA-C, BA-D, of which two designate each pole.
Section 5 pushes the variable-electron idea to its limit: inert gases have no extra-nuclear electrons at all, their spectra being artefacts of high-energy excitation. Liquid helium then follows without superfluidity — He-I is atoms settled under gravity with no interatomic attraction, hence no surface tension or viscosity; He-II arrests the residual vibration; the creeping film is a monoatomic layer responding to gravity. Superconductivity and the Meissner effect are complete charge subsidence together with continuous atomic contact, which predicts advantages for closed-shell metals such as lead, for mixed oxides, for boron nitride, and ideally for "a fluorine-containing metallic polymer like a continuous thread of teflon."
Section 6 applies charge subsidence to Taleyarkhan's sonofusion results, arguing that the authors' own explanation — millions of atmospheres and comparable temperatures at bubble collapse — "violates common sense," and proposing instead that sonic fission of the C–D bond in deuterated acetone gives deuterium radicals which undergo charge subsidence to dineutrons, uncharged and therefore free to approach within range of the strong force. He notes that subsidence should be easier when cold and that fusion is observed near 0 °C, and concludes that "Coulomb repulsion is an over-rated obstruction for fusion."
Sections 7 and 8 close the argument: proton sites in the nucleus may lie on its surface and coincide with covalent bonding sites, and the "central dogma" that the nucleus is an inert point charge with no influence on electron behaviour is rejected for chemical systems. He ends by citing J. T. Cushing's Quantum Mechanics: Historical Contingency and the Copenhagen Hegemony for the claim that the probabilistic interpretation was accepted through "social contingency."
Assessment
The paper is at its strongest where it stays close to chemistry and to a real historical fact: the aufbau scheme genuinely does require repair at almost every turn, and the repairs really were introduced case by case. Hybridisation, the three-centre two-electron bond and the Dewar–Chatt–Duncanson donation/back-donation scheme were each devised to accommodate a class of compounds that the preceding picture did not cover, and a working chemist's irritation at being asked to treat these as predictions rather than accommodations is not unreasonable. The observation that the 4s-below-3d ordering is often taught as an explanation when it is a fitted result is fair. The chirality problem is also a real one with a real literature — Woolley's "must a molecule have a shape?" question is a serious foundational puzzle about how a definite nuclear framework emerges from a Coulomb Hamiltonian that has none — and Balasubramanian deserves credit for pointing readers at it rather than inventing a grievance.
But the treatment of that literature is where the paper's method breaks down. Woolley's argument is that molecular structure is not given by the isolated-molecule Hamiltonian and must emerge from the environment and from the Born–Oppenheimer separation; it is an argument about where structure comes from, not a demonstration that chirality is impossible. Balasubramanian reads a foundational subtlety as a flat refutation, and this pattern recurs. The σ-donation/π-back-donation objection is not sound: nothing in that description involves a closed cycle returning to the same state, since the ligand and metal orbitals are different orbitals and the net result is a single bound state at lower energy than the separated fragments — the perpetual-motion conclusion does not follow. Similarly, the inference from volatility to electron count runs the wrong way: SF6 and UF6 are volatile because they are non-polar, closed, roughly spherical molecules with weak dispersion forces and no available lone-pair or dipole interactions, which is a statement about intermolecular forces, not about how many electrons are present. Their electron counts are directly constrained by measurement — X-ray and electron diffraction structure factors, photoelectron spectra, and simple mass and charge balance in their syntheses.
Several claims conflict with established measurement in ways the paper does not confront. The proposal that inert gases have no extra-nuclear electrons is contradicted by the photoelectron spectrum of argon, which shows 3p and 3s ionisation energies at 15.76 and 29.24 eV, by argon's X-ray scattering factor, and by the existence of compounds such as XeF4, whose structure has been determined crystallographically. The account of liquid helium as atoms merely "settled under gravity" cannot accommodate the lambda transition at 2.17 K, which shows a sharp specific-heat anomaly — a phase change of exactly the kind he denies occurs — nor the quantised vortices and second sound observed in He-II. The claim that current cannot be carried by massive particles confuses signal velocity with carrier velocity: the electromagnetic signal travels near c while the electron drift velocity in copper is of order millimetres per second, a distinction directly measured in the Hall effect and in the Tolman–Stewart experiment, which detects the inertia of the charge carriers and gives their charge-to-mass ratio as the electron's. The skin effect he cites as evidence for a helical field is quantitatively predicted by Maxwell's equations with ordinary conduction. And Taleyarkhan's sonofusion results, invoked in Section 6 as an established phenomenon, were not independently replicated and were the subject of a research-misconduct finding at Purdue in 2008.
The deeper weakness is structural. The Unitary Model is asserted, never derived, and it makes no quantitative prediction anywhere in sixteen pages — no bond length, no ionisation energy, no spectral line. Charge "rise and subsidence" is invoked to explain volatility, superconductivity, inert-gas behaviour and cold fusion alike, without any rule saying when charges subside or by how much, which makes it unfalsifiable in exactly the way the paper accuses hybridisation of being. A critique whose central complaint is that orthodoxy patches each new case with a fresh assumption is obliged to do better, and this one substitutes a single elastic assumption for many specific ones. Read as a list of places where textbook quantum chemistry is taught as though it explained more than it does, the paper has some value; read as the refutation its title promises, it does not carry the argument.