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Many-Body Problem (2022 Edition)


Contents

Quantum Mechanics :
   Hartree Fock Method (HF)
   Molecular Orbital
   Density Functional Theory (DFT)
   Diatomic Moleucle
   Band Theory
Plasma Physics (Fluid Dynamics)
Ideal Gas and Real Gas (Thermodynamics)
Newtonian Mechanics :
   Constant Gravity
   Reduced Mass
   Planetary Motion
   Three-Body Problem
   Rigid Body
   Space Flight

In both classical and quantum physics, exact solution in closed form can be obtained only in system involving 1 or at most 2 particles. However, there are infinite number of particles in the real world. Under the title of "Many-Body Problem", various kinds of approximates
Many-Body System are employed to evaluate the physical properties. The followings use the Many-Body Schrodinger equation to illustrate how it is done to extract information about the many-body systems from individual atom to solid (Figure 01), then expanding to macroscopic systems and gravity.

Figure 01 Many-Body System
[view large image]


Hartree Fock Method (HF)

The full glory of Schrodinger equation for many-body system is shown in Figure 02. It is intractable for system of more than 2 particles. An immediate simplification is to separate the system into 2 parts - one for the electrons and the other for the nuclei because electrons moves much faster, its motion is almost independent of the nuclear movement. This is called Born-Oppenheimer Approximation.
Schrodinger Equation

Figure 02 Schrodinger Equation, Many-Body [view large image]

See Figure 10 for a pictorial portrait of Ue(R).


The electronic Hamiltonian is simplified further by removing VNN which is just a constant for the fixed set of nuclear coordinates Rab. The requirement of antisymmetry (Pauli's Exclusion) principle for the wave function is satified in the form of Slater determinant :

Under these modifications, the electronic energy Ue is replaced by the Hartree Fock energy EHF (see Eq.(1)) :
Stationary Orbital

Figure 03 Stationary Orbital
[view large image]

See "An Introduction to Hartree-Fock Molecular Orbital Theory" for the original derivation, "Stationary-action principle", and "Lagrange multiplier".

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Molecular Orbital

Molecular Orbital

Figure 04 H2 Molecular Orbitals [view large image]

See "definition of F(x1) in Eq.(4a)".



Since the Coulomb integral Faa is negetive, the ordering in energy levels is correct in Figure 04 for the case of parallel spin.

The above example is applicable to the (H2)+ molecule, one electron of which has been dispatched to infinity. It is similar to the case of atomic hydrogen ion (proton) H+ for which all the energy levels have been calculated by solving the Schrodinger equation (with M = 1, N = 1 instead of M = 2, N = 2, see Figure 02) exactly. See "Molecular Orbital Theory" for more H2 molecular orbitals.

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Density Functional Theory (DFT)

The Density Functional Theory (DFT) replaces the individual electrons with one electron density greatly simplified the formulation as shown in Figure 05. The theory takes advantage of the fact that it is not necessary to know the wave functions of all N electrons. Knowledge of one or two interacting electrons is sufficient, i.e, one form fits all (each term looks the same as the others). Thus, the electronic Hamiltonian He (in Eq.(1), minus VNN) has this explicit mathematical form :
Density Functional Theory (DFT)

Figure 05 Density Functional Theory (DFT) [view large image]

There are two problems with this formulation :
(1) It fails to incorporate the density n(r1) into the kinetic energy term Te.
(2) It does not support the exchange energy Eex (the last term in Eq.(10b).
These problems are addressed variably by trial orbital or fictitious electron density. The "Local Density Approximation (LDA)" is selected as an example here. For evaluating the kinetic energy Te, the scheme is to place N non-interacting electrons in to a box of volume, V, with a positive background charge keeping the system neutral, i.e., the electron density n = N/V = constant (see Figure 06).
Local Density Approximation (LDA)

Figure 06 Local Density Approximation

See "Figure 06, and Density of States, Fermi Energy and Energy Bands".


r and k Space of Lattice

Figure 07 r and k Space of Lattice [view large image]

See "Figure 07, and Solid State Physics" for Reciprocal Lattice.


Stationary Density Returning to the interacting electrons, it is assumed that the density dependence (in exponential power) is similar to the non-interacting case. Thus, according to Eqs. (10,a,b), (14) and (15b), the electron energy can be expressed as the functional of n :
Ue[n] = VeN[n] + Te[n] + Vee[n] ---------- (16a)
Similar to the HF Method, the DFT's ultimate task is to minimize Ue[n] together with the constraint
P = n(r)d3r - N = 0, i.e.,
L[n] = 0 ---------- (16b),
where L[n] = Ue[n] - P[n] ---------- (16c).

Figure 08 Stationary
Density

See Figure 08.


In addition, there is this so-called Correlation interaction, which is also a result of the Pauli Exchange interaction. In the absence of precise knowledge of its nature, it is often assumed that its energy Ec is the error between the exact ground state energy E0 and approximate calculation, i.e.,
Ec = E0 - Ue ---------- (17).

By early 21 century, attempts are made to link the correlation interaction with entanglement. Here's one example to calculate Ue = EHF with the HF method and thus Ec from Eq.(17). Then uses the same method to compute the single-electron density n(r1)/N in Eq.(11a). The nomenclature in "entanglement" research uses (x,x') instead of n(r1)/N. The single electron coordinate r1 has split into x and x' to represent 2 opposite spin states and (x,x') becomes a matrix called "density matrix" (see "von Neumann Entropy").
The von Neumann entropy S() is the quantum version of the "Shannon's Measure of Information" :
SMI = - i pilog2(pi), i.e.,
S() = -Tr[n()] ---------- (18),
where Tr is the trace of the matrix.
Ec and Entanglement

Figure 09 Entanglement and Ec [view large image]

Entanglement Measure and EHF (and thus Ec from E.(17)) has been calculated for 10 Helium-like atoms, e.g., H-, He, ... Ne+8 as shown in Figure 09. It shows a definite correlation between the 2 entities (see original article on "Correlation energy as a measure of non locality")

Although entanglement between microscopic particles lasts for very short interval of few seconds or less, it is very important in "quantum computing" (see more in "Entanglement and Teleportation").

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Diatomic Molecular

As shown in Figure 04,a, the 2 low laying electronic states of H2 have energy Ue(R), which becomes the potential energy to confine the atomic nuclei (Figure 10,a). There are various theoretical models to provide analytical approximation to the real thing. The simplest one is the Harmonic Oscillator, which is suitable for a range near the minimum of the potential curve (see Figures 10,b, and 11).

The Harmonic Oscillator is one of the basic ingredients of quantum mechanics. Its solutions are in closed form which enables relatively easy visualization. The usefulness is derived from the Taylor expansion of any function including the potential energy curve Ue :
Potential Curve
The second term with the first derivative tends to vanish near the minimum of any function, while the first term is a constant which would not affect the physics. Thus, only the quadruple term survives with the other terms being negligibly small and this is precisely the form for the potential energy of the harmonic oscillator.

Figure 10 Potential Curve [view large image]

Thus, Ue = k(R-Re)2/2, where k =[d2Ue/dR2]R=Re ---------- (20).


Quantum Harmonic Oscillator The Harmonic Oscillator Schrodinger equation
Hn = (p2/2m + m2x2/2)n = Enn ---------- (21),
where p = -i d/dx, and 2 = k/m. The eigen value (energy level) is En = (n + 1/2) . The zero point energy /2 usually is subtracted from the formula to avoid infinite energy in the vacuum. The wave functions can be expressed in terms of the Hermite Polynomials Hn(x), i.e., n(x) = Cn e-x2Hn. The explicit forms for few low lying states are shown in Figure 11. The formulation of quantum harmonic motion is useful in studying the vibrational modes of molecules and crystal lattice.

Figure 11 Quantum SHM Wave Functions [view large image]

The Morse curve Ue = De[1 - e-a(R-Re)]2 ---------- (22)
(see Figure 10,b) is a more realistic model, where De is the dissociation energy at R ,
"a" determines the width of the curve, and Re is derivated from dUe/dR = 0.
Energy Levels In presenting the potential curve for a diatomic molecule, one of the atomic nuclei is usually fixed at the origin of the coordinate frame. The other nucleus is then portrayed as vibrating and rotating inside the potential well as shown in Figure 10. The vibration is restricted to discrete energy levels. Each of the vibrational energy level v is further split into a series of rotational energy levels J called vibrational band. When the Schrodinger equation of Eq.(21) is expressed in spherical coordinates, separation of the spatial variables and wave functions into Y(R), (), and Z() turns it into 3 equations :

Figure 12 Energy Levels
[view large image]


See Figure 12,a for energy levels and "Associated Legendre Polynomials"; while YJmJ = PJmJ eimJ is called Spherical Harmonic.

The electric dipole transition is the dominant effect of the interaction between the electrons in a molecule with the electromagnetic field. The transition probability amplitude from an initial state to a final state ' is in the form :


The integral in Eq.(25) with the overlapping vibrational wave functions v is the essence of the "Franck-Condon" principle. In layman's language, it states that the preferred transition occurs when the initial and final wave functions overlap more significantly. This condition is satisfied most often at the turning points, where the momentum is zero as shown by the (blue, green) transition arrows in Figure 10,b).

Transitions are also governed by selection rules, which usually allow transitions to occur only between change of the rotational or vibrational quantum number by an amount of 0 or 1 at a time. Mathematically, it is the transition probability in Eq.(25) that determines whether a transition would occur. Here's a simple example of transition induced by the z-component of e, i.e., z = e cos() :

Similar consideration shows that the selection rule for Harmonic Oscillator is v = 1. The electronic selection rule should abide to those for rotation, vibration, plus total spin S = 0. See Figure 12b, "Selection Rules" and "Selection rules and transition moment integral".

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Band Theory

Band Theory About 80% of the free elements at room temperature exists in the form of metal. The conditions to form metal are vacant valence orbitals and low ionization energies. Similar to the splitting of energy levels when two or more atoms come close to each other; (See Figure 04.) energy levels broadened to a band (many closely spaced energy levels) for an aggregate of many atoms as shown in Figure 13,a.

Figure 13 Band Theory
[view large image]

See "Solid State Physics".


Due to the "Exclusion Principle" or equivalently the "Fermi-Dirac statistics", the valence electrons from the sodium atoms cannot occupy the same energy level of each others, they fill up the energy bands up to half of the 3s band at 0K (because the 3s level is only half filled, it can accommodate 2 electrons but there's only 1 in sodium atom), at an energy called Fermi energy EF. Figure 13,b shows that if there is empty levels available in the energy band, the valence electrons will be able to roam among the space in between the atoms by absorbing energy from the environment when the temperature is above 0K. With a few exceptions, metals have a silvery-white color because they reflect all frequencies of light. They have high electrical and thermal conductivity and all metals can be drawn into wires or hammered into sheets without shattering, i.e., they are ductile and malleable. These attributes are the result of mobile, non-rigid electron gas within the lattice. Most metals (except gold, silver, platinum, and diamond) do not occur as free elements in the Earth's crust. They are usually found in chemical combination with other elements as mineral ores. Figure 13,b also shows that in an insulator, the valence band is full and the next empty energy band is separated by a large energy gap. Conduction cannot occur unless some of the electrons in the valence band are promoted to the conduction band. Energy needed to promote a few electrons might be provided by heating the solid to a very high temperature or by shining X rays on it. No solid can remain a good insulator while it is exposed to X rays. A semi-conductor has a smaller energy gap. Electrons can be promoted to the conduction band as a result of irradiation such as the conversion of sunlight to electricity by means of a silicon cell.

Band Gap Doping The formation of band structure as shown in Figure 13,a is based on the model of "Free Electrons". Actually, there are atomic nuclei, which is characterized by periodic separation "a" with a corresponding potential VG(r) = VG(r+a). As shown in Figure 13,c and its magnifying version in Figure 14, for most values of the variable k = 2/, the electron energy E0 = 2k2/2me. Only at k = n/a, the energy splits to EG = E0 VG(k), where VG(k) is the Fourier transform of VG(r). This is the origin of the "Band Gap".

Figure 14 Band Gap [view large image]

Figure 15 Semiconductor Doping [view large image]

However, the band gap can be altered by in-purity doping which has the effect of narrowing the band gap as shown in Figure 15 either by adding electrons or introducing holes in the conduction band. This is the idea of semi-conductor.

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Plasma Physics

Plasma Physics Plasma is the fourth state of matter in which the components of the atom become separated. It is not produced by phase change. Its production depends on the separation of the atomic nuclei and electrons. Once detached, they move around independently and form a globally neutral mixture. Plasma is found in the stars and the interstellar environment making up most of our universe (~ 99 %, = 100% in early universe) under a wide range of temperature and density (Figure 16a). However, such condition does not occur frequently on Earth and that's why life can exists here. In our everyday life, plasmas have many applications (including nuclear-fusion, micro-electronics, television flat screens and so on), of which the commonest is the neon tube.

The Schrodinger equation is useless in describing the dynamics of plasma. The equations of motion are prescribed by the "Navier-Stokes Equations" in fluid dynamics.

Figure 16a Plasma Physica
[view large image]

There is no problem with the Quantum Theory, the failure of the Schrodinger equation in this case only reflects that different platform is used to describe different system by the reductionist's approach. It employs different method/theory for each different level and merge the various levels together at the ends. Usually the connection is to adopt the derived quantities or properties at the lower (smaller size) level
Some Reductionist's Systems as input parameters or established facts from the theory for the higher (larger size) level. Details in the lower level can be neglected by the theories for higher levels (such methodology is called "Effective Theory"). Figure 16b illustrates some of the systems according to the size of their components. The classification is incomplete as there are many more systems below, above, and in between.

Figure 16b Reductionist's Systems [view large image]

Anyway, here's an example of "Magnetohydrodynamics (MHD) and the Formation of Jet from Black Hole" :

Black Hole Schematic Nobody has seen a black hole until the silhouette in M87, 2019. Nevertheless, schematic diagram such as the one shown in figure 16c invariably presents a system composed with a central object (the black hole), an accretion disk, and a pair of jets moving along twisted magnetic field lines. This picture of the black hole is based theoretically on the combination of three branches of physics - Fluid Dynamics, Electromagnetism, and Gravitation.

The effect of gravity from the black hole is characterized by the escape velocity vesc(r) = (2GM/r)1/2, where M is the mass of the black hole, and r = (R2 + Z2)1/2 provides a link between the spherical and cylindrical coordinates (see upper left corner insert in Figure 16c).

With the assumptions of infinite conductivity (for the plasma in the system), isotropic pressure, local charge neutrality, non-relativistic inter-particle speeds), the suite of MHD equations are :

Figure 16c Black Hole Schematic [view large image]


These set of equations can be solved only through numerical computation. In general, the magnetic field has only the z component Bz initially. When the accretion disk is set into rotation, the field lines is wrapped around the rotation axis creating the helical field in the z direction. As ionized matter cannot cross field lines, it is obliged to follow the lines and thus form a collimated jet (Figure 23). The following is a scenario of the numerical computation according to a letter in Nature with the title "A magnetic switch that determines the speed of astrophysical jets".