, which are relevant to properly describe phenomena such as molecular dissociation with density-functional theory, to the case in which the electronic wavefunction corresponds to a complex current-carrying state. In such a case, an extra term in the form of a vector potential appears which cannot be gauged away. Both scalar and vector potentials are introduced via the exact factorization formalism which allows us to express the given Schrödinger equation as two coupled equations, one for the marginal and one for the conditional amplitude. The electronic vector potential is directly related to the paramagnetic current density carried by the total wavefunction and to the diamagnetic current density in the equation for the marginal amplitude. An explicit example of this vector potential in a triplet state of two non-interacting electrons is showcased together with its associated circulation, giving rise to a non-vanishing geometric phase. Some connections with the exact factorization for the full molecular wavefunction beyond the Born-Oppenheimer approximation are also discussed.
, which are relevant to properly describe phenomena such as molecular dissociation with density-functional theory, to the case in which the electronic wavefunction corresponds to a complex current-carrying state. In such a case, an extra term in the form of a vector potential appears which cannot be gauged away. Both scalar and vector potentials are introduced via the exact factorization formalism which allows us to express the given Schrödinger equation as two coupled equations, one for the marginal and one for the conditional amplitude. The electronic vector potential is directly related to the paramagnetic current density carried by the total wavefunction and to the diamagnetic current density in the equation for the marginal amplitude. An explicit example of this vector potential in a triplet state of two non-interacting electrons is showcased together with its associated circulation, giving rise to a non-vanishing geometric phase. Some connections with the exact factorization for the full molecular wavefunction beyond the Born-Oppenheimer approximation are also discussed.
There are different ways to obtain an exact one-electron theory for a many-electron system, and the exact electron factorization (EEF) is one of them. In the EEF, the Schrödinger equation for one electron in the environment of other electrons is constructed. The environment provides the potentials that appear in this equation: A scalar potential vH representing the energy of the environment and another scalar potential vG as well as a vector potential that have geometric meaning. By replacing the interacting many-electron system with the non-interacting Kohn-Sham (KS) system, we show how the EEF is related to density functional theory (DFT) and we interpret the Hartree-exchange-correlation potential as well as the Pauli potential in terms of the EEF. In particular, we show that from the EEF viewpoint, the Pauli potential does not represent the difference between a fermionic and a bosonic non-interacting system, but that it corresponds to vG and partly to vH for the (fermionic) KS system. We then study the meaning of vG in detail: Its geometric origin as a metric measuring the change of the environment is presented. Additionally, its behavior for a simple model of a homo- and heteronucler diatomic is investigated and interpreted with the help of a two-state model. In this way, we provide a physical interpretation for the one-electron potentials that appear in the EEF and in DFT.
The Born-Oppenheimer electronic wave function ${\mathrm{\ensuremath{\Phi}}}_{R}^{\text{BO}}(r)$ picks up a topological phase factor $\ifmmode\pm\else\textpm\fi{}1$, a special case of Berry phase, when it is transported around a conical intersection of two adiabatic potential energy surfaces in R space. We show that this topological quantity reverts to a geometric quantity ${e}^{i\ensuremath{\gamma}}$ if the geometric phase $\ensuremath{\gamma}=\ensuremath{\oint}\mathrm{Im}\ensuremath{\langle}{\mathrm{\ensuremath{\Phi}}}_{R}|{\mathbf{\ensuremath{\nabla}}}_{\ensuremath{\mu}}{\mathrm{\ensuremath{\Phi}}}_{R}\ensuremath{\rangle}\ifmmode\cdot\else\textperiodcentered\fi{}d{\mathbf{R}}_{\ensuremath{\mu}}$ is evaluated with the conditional electronic wave function ${\mathrm{\ensuremath{\Phi}}}_{R}(r)$ from the exact electron-nuclear factorization ${\mathrm{\ensuremath{\Phi}}}_{R}(r)\ensuremath{\chi}(R)$ instead of the adiabatic function ${\mathrm{\ensuremath{\Phi}}}_{R}^{\text{BO}}(r)$. A model of a pseudorotating triatomic molecule, also applicable to dynamical Jahn-Teller ions in bulk crystals, provides examples of nontrivial induced vector potentials and molecular geometric phase from the exact factorization. The induced vector potential gives a contribution to the circulating nuclear current that cannot be removed by a gauge transformation. The exact potential energy surface is calculated and found to contain a term depending on the Fubini-Study metric for the conditional electronic wave function.
We combine the recently developed many-body Green's function theory for electrons and nuclei with the exact factorization of the wave function. The existing Born-Oppenheimer Green's functions are shown to be special cases of our exact approach. We consider the limitations of the laboratory frame formulation of the Green's function theory and discuss why the body-fixed frame formulation is needed in order to go beyond the Born-Oppenheimer theory. We give exact forms of the electronic and nuclear Green's functions written in terms of the exact factorized states, providing a systematic approach beyond the Born-Oppenheimer approximation. The lowest order approximation to the exact electronic Green's function is found to be an expected value of the Born-Oppenheimer electronic Green's function with respect to the nuclear density.
Physical processes are usually described using four-dimensional vector quantities - coordinate vector, momentum vector, current vector. But at the fundamental level they are characterized by spinors - coordinate spinors, momentum spinors, spinor wave functions. The propagation of fields and their interaction takes place at the spinor level, and since each spinor uniquely corresponds to a certain vector, the results of physical processes appear before us in vector form. For example, the relativistic Schrödinger equation and the Dirac equation are formulated by means of coordinate vectors, momentum vectors and quantum operators corresponding to them. In the Dirac equation a step forward is taken and the wave function is a spinor with complex components, but still coordinates and momentum are vectors. For a closed description of nature using only spinor quantities, it is necessary to have an equation similar to the Dirac equation in which momentum, coordinates and operators are spinors. It is such an equation that is presented in this paper. Using the example of the interaction between an electron and an electromagnetic field, we can see that the spinor equation contains more detailed information about the interaction than the vector equations. This is not new for quantum mechanics, since it describes interactions using complex wave functions, which cannot be observed directly, and only when measured goes to probabilities in the form of squares of the moduli of the wave functions. In the same way spinor quantities are not observable, but they completely determine observable vectors. In Section 2 of the paper, we analyze the quadratic form for an arbitrary four-component complex vector based on Pauli matrices. The form is invariant with respect to Lorentz transformations including any rotations and boosts. The invariance of the form allows us to construct on its basis an equation for a free particle combining the properties of the relativistic wave equation and the Dirac equation. For an electron in the presence of an electromagnetic potential it is shown that taking into account the commutation relations between the momentum and coordinate components allows us to obtain from this equation the known results describing the interactions of the electron spin with the electric and magnetic field. In the presence of a potential the momentum components cease to commute with each other. To neutralize this effect, the Schrödinger equation is supplemented by several equations with mixed partial derivatives on coordinates. In section 3 of the paper this quadratic form is expressed through momentum spinors, which makes it possible to obtain an equation for the spinor wave function in spinor coordinate space by replacing the momentum spinor components by partial derivative operators on the corresponding coordinate spinor component. Section 4 presents a modification of the theory of the path integral, which consists in considering the path integral in the spinor coordinate space. The Lagrangian densities for the scalar field and for the electron field, along with their corresponding propagators, are presented. An equation of motion for the electron is proposed that is relativistically invariant, in contrast to the Dirac equation, which lacks this invariance. This novel equation permitted the construction of an actually invariant procedure for the second quantization of the fermion field in spinor coordinate space. Furthermore, it is demonstrated that the field operators are a combination of plane waves in spinor or vector space, with the coefficients of which being pseudospinors or pseudovectors. Each of these pseudovectors or pseudospinors corresponds to one of the particles presented in the theory of electrodynamics. Furthermore, each plane wave possesses an additional coefficient in the form of a creation or annihilation operator. In vector space, these operators commute, whereas in spinor space they anticommutate. The paper presents the spinor and vector representations of the field operators in explicit form, comprising sets of 16 pseudospinors or 4 pseudovectors corresponding to particles represented in electrodynamics. An explicit form of the symmetric traceless tensor with spin two, zero mass and two polarizations is presented, which can serve as a model of the graviton. The results obtained may prompt changes in some aspects of the construction of Feynman diagrams. Among other things, it presents a purely mathematical derivation of Maxwell's inhomogeneous equations without reference to empirical data on the action of electric current, which is usually referred to when deriving equations. Section 4 presents Einstein's inhomogeneous equation, which features the Riemann tensor rather than the Ricci tensor, with the energy-momentum tensor having four indices rather than two.
Physical processes are usually described using four-dimensional vector quantities - coordinate vector, momentum vector, current vector. But at the fundamental level they are characterized by spinors - coordinate spinors, momentum spinors, spinor wave functions. The propagation of fields and their interaction takes place at the spinor level, and since each spinor uniquely corresponds to a certain vector, the results of physical processes appear before us in vector form. For example, the relativistic Schrödinger equation and the Dirac equation are formulated by means of coordinate vectors, momentum vectors and quantum operators corresponding to them. In the Dirac equation a step forward is taken and the wave function is a spinor with complex components, but still coordinates and momentum are vectors. For a closed description of nature using only spinor quantities, it is necessary to have an equation similar to the Dirac equation in which momentum, coordinates and operators are spinors. It is such an equation that is presented in this paper. Using the example of the interaction between an electron and an electromagnetic field, we can see that the spinor equation contains more detailed information about the interaction than the vector equations. This is not new for quantum mechanics, since it describes interactions using complex wave functions, which cannot be observed directly, and only when measured goes to probabilities in the form of squares of the moduli of the wave functions. In the same way spinor quantities are not observable, but they completely determine observable vectors. In Section 2 of the paper, we analyze the quadratic form for an arbitrary four-component complex vector based on Pauli matrices. The form is invariant with respect to Lorentz transformations including any rotations and boosts. The invariance of the form allows us to construct on its basis an equation for a free particle combining the properties of the relativistic wave equation and the Dirac equation. For an electron in the presence of an electromagnetic potential it is shown that taking into account the commutation relations between the momentum and coordinate components allows us to obtain from this equation the known results describing the interactions of the electron spin with the electric and magnetic field. In the presence of a potential the momentum components cease to commute with each other. To neutralize this effect, the Schrödinger equation is supplemented by several equations with mixed derivatives on coordinates. In section 3 of the paper this quadratic form is expressed through momentum spinors, which makes it possible to obtain an equation for the spinor wave function in spinor coordinate space by replacing the momentum spinor components by partial derivative operators on the corresponding coordinate spinor component. Section 4 presents a modification of the theory of the path integral, which consists in considering the path integral in the spinor coordinate space. The Lagrangian densities for the scalar field and for the electron field, along with their corresponding propagators, are presented. An equation of motion for the electron is proposed that is relativistically invariant, in contrast to the Dirac equation, which lacks this invariance. This novel equation permitted the construction of an actually invariant procedure for the second quantization of the fermion field in spinor coordinate space. Furthermore, it is demonstrated that the field operators are a combination of plane waves in spinor or vector space, with the coefficients of which being pseudospinors or pseudovectors. Each of these pseudovectors or pseudospinors corresponds to one of the particles presented in the theory of electrodynamics. Furthermore, each plane wave possesses an additional coefficient in the form of a creation or annihilation operator. In vector space, these operators commute, whereas in spinor space they anticommutate. The paper presents the spinor and vector representations of the field operators in explicit form, comprising sets of 16 pseudospinors or 4 pseudovectors corresponding to particles represented in electrodynamics. An explicit form of the symmetric traceless tensor with spin two, zero mass and two polarizations is presented, which can serve as a model of the graviton. The results obtained may prompt changes in some aspects of the construction of Feynman diagrams. Among other things, it presents a purely mathematical derivation of Maxwell's inhomogeneous equations without reference to empirical data on the action of electric current, which is usually referred to when deriving equations.