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Deterministic quantum mechanics: Why is nuclear motion classical?

Irmgard Frank

Published Jul 28, 2025• 0 citations
Publisher

Abstract

Quantum mechanics is perceived as a theory that is difficult to understand with strange philosophical consequences. This is due to the Copenhagen interpretation of quantum mechanics. On the basis of the knowledge accumulated in modern computer simulations of many-particle problems, a different approach is presented that is purely deterministic. To arrive at this simpler picture, it is sufficient to treat nuclear motion classically. It is argued that this is justified by the different nature of nuclear motion compared to electronic structure, which must be described quantum-mechanically. The underlying approximation leads directly to the theory that is mainly used nowadays to simulate chemical reactions. As a result, electronic structure develops with time without any wavefunction collapse.

DOI
10.26434/chemrxiv-2025-87vsj

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Quantum mechanics is perceived as a theory that is difficult to understand with strange philosophical consequences. This is due to the Copenhagen interpretation of quantum mechanics. On the basis of the knowledge accumulated in modern computer simulations of many-particle problems, a different approach is presented that is purely deterministic. To arrive at this simpler picture, it is sufficient to treat nuclear motion classically. It is argued that this is justified by the different nature of nuclear motion compared to electronic structure, which must be described quantum-mechanically. The underlying approximation leads directly to the theory that is mainly used nowadays to simulate chemical reactions. As a result, electronic structure develops with time without any wavefunction collapse.
The application of modern quantum chemical methods to the simulation of chemical reactions makes it obvious that the Copenhagen picture of quantum mechanics cannot be maintained. In ab-initio molecular dynamics methods, any kind of matter is described by applying the Schrödinger equation to the electronic structure and using classical Newton dynamics for the motion of the atomic nuclei. By lots of calculations on this basis, it has become obvious that this concept is superior to a quantum chemical description of nuclear motion. The nuclei move according to Newton's laws in a perfectly local and deterministic way while the surrounding electronic cloud determines bonding and antibonding interactions between the atoms. The resulting theory is a deterministic formulation of quantum mechanics which is free from paradoxa and is able to explain complex phenomena like photochemistry. An obvious consequence is that molecules like ammonia can have a permanent dipole moment in spectroscopic measurements, while consistent application of traditional quantum mechanics predicts a higher symmetry as is outlined in the paper.
It is argued that although quantum theory isn't an absolutely deterministic theory, it is partially deterministic. The approach followed here is in the framework of the standard (Copenhagen interpretation of) quantum mechanics without any additional assumption or alternative interpretation. The argument is based on the conceptual meaning of determinism and by means of some well-known phenomena in the quantum world (measurement of a quantum particle spin, energy values and spatial states of an electron in atoms, the so-called wavefunction collapse problem) which are usually considered in rejecting determinism.
Abstract To be accepted by the community, the claim that nuclear motion has to be treated classically must be tested for all kinds of phenomena. For the moment we claim that in a quantum chemical calculation, a classical description of nuclear motion is superior to the use of the Schrödinger equation, and investigate how far we get with this statement. In the present paper we address the question what nuclear quantum statistics means in this context. We will show that the Maxwell–Boltzmann velocity distribution evolves quickly in any molecular dynamics simulation and this guarantees the physically correct behavior of molecular systems. Using first‐principles molecular dynamics simulations, or more precisely Car–Parrinello molecular dynamics, we investigate what this means for Bose‐Einstein condensates and for Cooper pairs. It turns out that our approach can explain all relevant phenomena. As a consequence, we can introduce a deterministic formulation of quantum mechanics and can get rid of all the paradoxa in traditional quantum mechanics. The basic idea is to treat electrons and nuclei differently.
The dominance of the Copenhagen interpretation is the result of a historical accident (Cushing, 1994). At the Solvay conference in 1927, Louis de Broglie put forward the deterministic pilot wave theory, described later. Never slow to criticize, Pauli jumped up and demolished de Broglie’s proposal, and de Broglie was so discouraged by this that he did not develop his interpretation any further. The Copenhagen interpretation was then developed by Bohr, Heisenberg, Pauli and many others, as described in the previous chapter. It was strongly supported by von Neumann’s proof of the impossibility of hidden variables. Years later, in 1952, Bohm published a deterministic hidden variable theory, showing that there must be something wrong with von Neumann’s proof. The error was found by John Bell in 1966, as described in the last chapter, and he also showed how Pauli’s objections to de Broglie’s original idea can be answered. If this had been done at the conference in 1927, quantum mechanics could have been interpreted deterministically from the beginning. The essential mistake in the Copenhagen interpretation is to treat it as a complete account of the behaviour of each individual system. It is frequently claimed that it enables us to calculate, at least in principle, everything that can be measured. Thus Hooft (1997, p. 11) said that ‘The laws of quantum mechanics have been formulated very accurately. We know exactly how to compute anything we would like to know.’ Also Peierls (1997, p. 25) has said that quantum mechanics ‘had become a complete and consistent scheme capable of giving a unique answer to any questions relating to actual or possible observations’. Even if this were true, it would not imply that it is the final complete theory, for it is always possible that some new phenomenon might be found that cannot be calculated quantum-mechanically. However, it is not true: there are many phenomena such as the time of decay of a radioactive nucleus, or the direction a particle is scattered by a nucleus, that cannot be calculated, even in principle. Quantum mechanics is therefore an incomplete theory. We can only calculate the statistical properties of these systems, such as the half-life of a radioactive decay or the differential scattering cross-section that gives the probabilities that a particle is scattered through various angles. All measurements of quantum systems are of this statistical character. It might be thought that the possibility of making measurements on a single electron provides an exception to this. However, even in such cases the electron is continually bathed in a fluctuating background radiation from nearby atoms. Since this is variable, that electron is a member of an ensemble of electrons subject to different fluctuations. All these examples clearly demonstrate the statistical character of quantum mechanics. ‘I am rather firmly convinced’, Einstein (in Schilpp, 1949, pp. 666, 671) remarked, ‘that the essentially statistical character of contemporary quantum theory is solely to be ascribed to fact that this theory operates with an incomplete description of physical systems’. As a result, ‘the c-function is to be understood as the description not of a single system but of an ensemble of systems’. So, ‘if the statistical quantum theory does not pretend to describe the individual system completely, it appears unavoidable to look elsewhere for a complete description of the individual systems’. Thus ‘the difficulties of theoretical interpretation disappear, if one views the quantum-mechanical description as a description of an ensemble of systems’. If this is achieved, ‘the statistical theory would, within the framework of future physics, take an approximately analogous position to statistical mechanics within the framework of classical mechanics’. ‘Thus, essentially, nothing has changed since Galileo or Newton or Faraday concerning the status of the ‘‘observer’’ or our ‘‘consciousness’’ or of our ‘‘information’’ in physics’ (Popper, 1982, p. 46). Once this is accepted, the quantum paradoxes that plagued the Copenhagen interpretation are easily resolved, as described below. In any textbook of quantum mechanics problems such as the calculation of the energy levels of the hydrogen atom are solved as if that hydrogen atom is alone in the universe. As Feynman (1972) remarked, ‘when we solve a quantum-mechanical problem, what we really do is to divide the universe into two parts – the system in which we are interested and the rest of the universe. We then usually act as if the system in which we are interested comprised the whole universe.’ In fact, however, every hydrogen atom on which measurements are made is surrounded by other atoms and exposed to their radiations. Quantum mechanics somehow takes this into account and gives the average behaviour of an ensemble of hydrogen atoms. A more detailed theory takes these influences into account. One attempt to do this is stochastic electrodynamics, described in a later section.
The present paper is based upon equations obtained in an earlier paper by the author devoted to a new formulation of quantum electrodynamics. The equations describe the structure of the electron as well as its motion in external fields, interaction with a measuring apparatus inclusive, in a deterministic manner without any jumps. Quantum mechanics is an approximate theory because its equations follow from the above equations upon neglecting the self-field of the electron itself. Just this leads to paradoxes, seeming contradictions and jumps in quantum mechanics. The quantum mechanical wavefunction has a dual interpretation. In some problems the square of its modulus represents a real distribution of the electronic density while in others the same square determines the probability distribution of coordinates. It is shown why, given the different interpretations of the wavefunction, it satisfies one and the same Dirac or Schrödinger equation. Description of many-electron systems is also considered in the starting approach as well as in quantum mechanics. Neutrinos are discussed in brief.
Abstract Despite the successful development of quantum chemistry, the deep breakdown between the conceptual basis of standard quantum mechanics and some implicit ontological assumptions of quantum chemistry is only rarely acknowledged. In fact, in the framework of standard quantum mechanics, quantum systems are not individual objects in the philosophical sense: they cannot be individualized by their positions in space and time and, as a consequence, they have no trajectories. By contrast, the basic magnitude in quantum chemistry is the electronic density, which is commonly interpreted in terms of the definite positions occupied by the individual electron in its motion around the nucleus. In the present paper, it will be argued that Bohmian Mechanics offers an ontological picture that is much closer to the quantum chemists’ way of conceiving their research field.