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Journal of Astrophysics & Aerospace Technology | ISSN: 2329-6542 | Volume 6
Atomic and Nuclear Physics
4
th
International Conference on
October 26-27, 2018 | Boston, USA
Where and why quantum mechanics ceases to work in molecular and chemical physics
Vladimir V Egorov
Russian Academy of Sciences, Russia
L
et’s turn to the basics of quantum mechanics. In atoms, the nucleus is essentially only a source of a potential electric field in which
electrons move. Quantum mechanics works here: we write a Hamiltonian for electrons in this field and solve the corresponding
Schrödinger equation. In molecules in a stationary state, where the adiabatic approximation works, on the contrary, electrons are
considered as a source of a potential electric field in which the nuclei vibrate.1 Here quantum mechanics also works, but the price of
this is the adiabatic approximation. Note that both in the former and in the latter cases, in essence one of the subsystems is “switched
off ” dynamically: in the case of atoms the nucleus is “turned off ”, and in the case of molecules the electrons are “turned off ”. Quantum
mechanics works in molecules only until the electrons are dynamically “off ”. As soon as we begin to consider molecular quantum
transitions, we are forced to treat electrons dynamically, that is, for transitions we already have two essential dynamical systems:
nuclei that oscillate, and electrons whose charge distribution changes during the transition. And both systems strongly (through
the Coulomb field) interact with each other. The whole “trouble” is that the mass of the electron is a colossal number of times
smaller than the mass of the nuclei. In molecules, in their essential dynamics, when there is a structural reorganization of the nuclear
subsystem in molecular quantum transitions, this fact leads to a singularity in the probabilities (per unit time) of quantum transitions.
This singularity means that the joint motion of electrons and nuclei, when both subsystems are dynamically full-fledged,2 can not
be regular. Therefore, this singularity must be damped by introducing chaos (dozy chaos) into dynamics of molecular quantum
transitions or elementary chemical reactions, which is done by the author. But after the damping procedure is introduced, the whole
theory ceased to be quantum mechanics: because of chaos in the intermediate dynamic state, we have a continuous spectrum of
energy in this state, which is a sign of classical mechanics. Shortly speaking, the physical nature of molecular quantum transitions is
associated with a certain, recently discovered, unique property of an electron that binds atoms to molecules. This property consists
in provoking by a light electron of chaos in the vibrational motion of very heavy nuclei “for the purpose” to control their motion
in the processes of molecular quantum transitions. Thus, an electron being a quantum micro-particle in an atom, which performs
quantum jumps, in a molecule in the processes of molecular quantum transitions, it acquires the features of a classical motion. In
the formal language, the situation is as follows. As is known, the theory of quantum transitions in quantum mechanics is based on
the convergence of a series of time-dependent perturbation theory. In atomic and nuclear physics, the quantum-mechanical series
of time-dependent perturbation theory converges because in the corresponding matrix elements of the transitions due to quantum
jumps the dynamics of quantum transitions is absent by definition. On the contrary, this series diverges in molecular and chemical
physics, since in these matrix elements the dynamics of “quantum” transitions, which is determined by the joint motion of a light
electron (or electrons) and very heavy nuclei, is already present by definition. Strictly speaking, only two methods can eliminate the
singularity in the quantum-mechanical series of time-dependent perturbation theory. The first method was proposed almost 100 years
ago and consisted essentially in refusing to consider the dynamics of molecular “quantum” transitions by introducing an additional
postulate in the form of the Franck-Condon principle into molecular quantum mechanics, in which the adiabatic approximation is
used. The second method was proposed by the author and consists in replacing the infinitely small imaginary additive in the energy
denominator of the total Green’s function of the molecular system by its finite value. It follows from a comparison of the new theory
with experiment that the modulus of this imaginary additive is much larger than the quantum of vibrations of the nuclei. This means
that in the process of quantum transitions there is an exchange of motion and energy between the electron and the nuclei, and this
exchange is so intense that chaos arises in the transient state. This chaos is called dozy chaos, since it is not present either in the initial
or final states, and it arises only during molecular quantum transitions. The effectiveness of the damping procedure for the above
singularity is demonstrated by the example of a new (dozy-chaos) theory of elementary electron-charge transfers in condensed media
and its applications to the optical band shapes in polymethine dyes and their aggregates.
egorov@photonics.ruJ Astrophys Aerospace Technol 2018, Volume 6
DOI: 10.4172/2329-6542-C3-024