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Apple Academic Press eBooks

Formalization of Quantum Mechanics

Mihai V. Putz

Published Mar 30, 2016• 0 citations
Publisher

Abstract

Abstract ................................................................................................... 66 2.1 Introduction .................................................................................... 66 2.2 Wave Function Picture ................................................................... 67 2.2.1 Green and Dirac Functions ................................................ 67 2.2.2 Momentum and Energy Operators ..................................... 69 2.2.3 Klein-Gordon and Schrödinger Equations ......................... 72 2.2.4 Electronic and Photonic Spins ........................................... 74 2.2.5 Eigen-Functions and Eigen-Values .................................... 75 2.2.6 Hermitic Operators ............................................................ 76 2.2.7 Heisenberg Uncertainty Theorem ...................................... 81 2.2.8 Ehrenfest Theorem ............................................................. 85 2.2.9 Current Density Probability Conservation Theorem ......... 89 2.3 Classical to Quantum Mechanics’ Correspondence ....................... 92 2.3.1 Classical Euler-Lagrange, Hamilton, and Hamilton-Jacobi Equations ................................................ 92 2.3.2 Wave-Function Quantum Field .......................................... 97 2.3.3 Semi-classical Expansion and the WKB Approximation ................................................................. 102 2.3.4 From Field Internal Symmetry to Current Conservation .................................................................... 106 2.3.5 From Poisson Parentheses to Quantum Commutators and Heisenberg Picture ............................. 108 2.4 Bra-ket (Dirac) Formalism ............................................................115 2.4.1 Vectors in Hilbert Space....................................................115 2.4.2 Linear Operators in Hilbert Space ....................................118 2.4.3 Spectral Representations of Vectors and Operators ......... 126 2.4.4 Coordinate and Momentum Representations ................... 136 2.4.5 Energy Representation ..................................................... 148 2.4.6 Heisenberg Matrix Quantum Mechanics: The Harmonic Oscillator ................................................. 151 2.5 Conclusion ................................................................................... 159 Keywords .............................................................................................. 160 References ............................................................................................. 161 Author’s Main Reference ............................................................. 161 Further Readings .......................................................................... 161 ABSTRACT Although equivalent to certain points, various approaches of quantum phenomena may add new insights and perspective on studied systems either in isolate or interaction states. Here, the main formalisms are reviewed and illustrated, especially those making the ground-nous of the quantum mechanics itself, i.e., the undulatory quantum mechanics, while introducing the quantum propagator (Green function) concept, the semi-classical approach based on Euler-Lagrange and Hamiltonian, while the bra-ket Dirac picture opens the new perspectives of further developing quantum theory by abstract yet logical and formalized reasoning.

DOI
10.1201/b21340-8

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Abstract ................................................................................................... 66 2.1 Introduction .................................................................................... 66 2.2 Wave Function Picture ................................................................... 67 2.2.1 Green and Dirac Functions ................................................ 67 2.2.2 Momentum and Energy Operators ..................................... 69 2.2.3 Klein-Gordon and Schrödinger Equations ......................... 72 2.2.4 Electronic and Photonic Spins ........................................... 74 2.2.5 Eigen-Functions and Eigen-Values .................................... 75 2.2.6 Hermitic Operators ............................................................ 76 2.2.7 Heisenberg Uncertainty Theorem ...................................... 81 2.2.8 Ehrenfest Theorem ............................................................. 85 2.2.9 Current Density Probability Conservation Theorem ......... 89 2.3 Classical to Quantum Mechanics’ Correspondence ....................... 92 2.3.1 Classical Euler-Lagrange, Hamilton, and Hamilton-Jacobi Equations ................................................ 92 2.3.2 Wave-Function Quantum Field .......................................... 97 2.3.3 Semi-classical Expansion and the WKB Approximation ................................................................. 102 2.3.4 From Field Internal Symmetry to Current Conservation .................................................................... 106 2.3.5 From Poisson Parentheses to Quantum Commutators and Heisenberg Picture ............................. 108 2.4 Bra-ket (Dirac) Formalism ............................................................115 2.4.1 Vectors in Hilbert Space....................................................115 2.4.2 Linear Operators in Hilbert Space ....................................118 2.4.3 Spectral Representations of Vectors and Operators ......... 126 2.4.4 Coordinate and Momentum Representations ................... 136 2.4.5 Energy Representation ..................................................... 148 2.4.6 Heisenberg Matrix Quantum Mechanics: The Harmonic Oscillator ................................................. 151 2.5 Conclusion ................................................................................... 159 Keywords .............................................................................................. 160 References ............................................................................................. 161 Author’s Main Reference ............................................................. 161 Further Readings .......................................................................... 161 ABSTRACT Although equivalent to certain points, various approaches of quantum phenomena may add new insights and perspective on studied systems either in isolate or interaction states. Here, the main formalisms are reviewed and illustrated, especially those making the ground-nous of the quantum mechanics itself, i.e., the undulatory quantum mechanics, while introducing the quantum propagator (Green function) concept, the semi-classical approach based on Euler-Lagrange and Hamiltonian, while the bra-ket Dirac picture opens the new perspectives of further developing quantum theory by abstract yet logical and formalized reasoning.
Abstract ................................................................................................. 359 4.1 Introduction .................................................................................. 359 4.2 Feynman’s Path Integral Quantum Formalism ............................ 364 4.2.1 Construction of Path Integral ........................................... 364 4.2.2 Propagator’s Equation ...................................................... 370 4.2.3 Recovering Wave Function’s Equation ............................ 373 4.3 Path Integrals for Basic Matter’s Structures ................................ 377 4.3.1 General Path Integral’s Properties ................................... 377 4.3.2 Path Integral for the Free Particle .................................... 384 4.3.3 Path Integral for Motion as the Harmonic Oscillator ...... 387 4.3.4 Path Integral Representation for the Bohr’s Atom ........... 394 4.3.5 Path Integral for Motion in the Quantum Well ................ 398 4.4 Density Matrix Approach Linking Path Integral Formalism ....... 402 4.4.1 On Mono-, Many-, and Reduced-Electronic Density Matrices .............................................................. 402 4.4.2 Canonical Density, Bloch Equation, and the Need of Path Integral ....................................................... 412 4.5 Roots of Self-Consistent Methods in Quantum Chemistry .......... 419 4.5.1 Molecular Orbital Approach ............................................ 420 4.5.2 Roothaan Approach .......................................................... 423 4.5.3 Introducing Semi-Empirical Approximations .................. 428 4.5.3.1 NDO Methods ................................................... 429 4.5.3.2 NDDO Methods ................................................ 432 4.5.4 Ab initio Methods: The Hartree-Fock Approach ............. 436 4.5.4.1 Hartree-Fock Orbital Energy ............................ 438 4.5.4.2 About Correlation Energy ................................. 442 4.5.4.3 Koopman’s Orbital Theorem with Hartree-Fock Picture ......................................... 444 4.5.4.4 Chemical Reactivity Indices in Orbital Energy Representation ...................................... 451 4.5.4.5 Testing Koopmans Theorem by Chemical Harness Reactivity Index .................. 458 4.6 Density Functional Theory: Observable Quantum Chemistry ..... 468 4.6.1 Hohenberg-Kohn theorems .............................................. 470 4.6.2 Optimized Energy-Electronegativity Connection ............ 475 4.6.3 Popular Energetic Density Functionals ............................ 480 4.6.3.1 Density Functionals of Kinetic Energy ............. 481 4.6.3.2 Density Functionals of Exchange Energy ......... 484 4.6.3.3 Density Functionals of Correlation Energy ...... 490 4.6.3.4 Density Functionals of Exchange-Correlation Energy ........................... 496 4.7 Observable Quantum Chemistry: Extending Heisenberg’s Uncertainty ............................................................. 502 4.7.1 Periodic Path Integrals ..................................................... 502 4.7.1.1 Effective Partition Function .............................. 502 4.7.1.2 Periodic Quantum Paths .................................... 505 4.7.2 Heisenberg Uncertainty Reloaded ................................... 508 4.7.3 Extending Heisenberg Uncertainty ...................................511 4.7.3.1 Averaging Quantum Fluctuations ......................511 4.7.3.2 Observed Quantum Evolution .......................... 514 4.7.3.3 Free Quantum Evolution ................................... 515 4.7.3.4 Free vs. Observed Quantum Evolution ............. 518 4.7.3.5 Spectral-IQ Method .......................................... 523 4.7.3.6 Spectral-IQ Results on Silica Sol-Gel-Based Mesosystems ..................................................... 527 4.8 Conclusion ................................................................................... 533 Keywords .............................................................................................. 535 References ............................................................................................. 536 Author’s Main References ........................................................... 536 Specific References ...................................................................... 537 Further Readings .......................................................................... 549 ABSTRACT Basing on the first principles of Quantum mechanics as exposed in the previous chapters and sections, special chapters of quantum theory are here unfolded in order to further extend and caching the quantum information from free to observed evolution within the matter systems with constraints (boundaries). As such, the Feynman path integral formalism is firstly exposed and then applied to atomic, quantum barrier and quantum harmonically vibration, followed by density matrix approach, opening the Hartree-Fock and Density Functional pictures of many-electronic systems, with a worthy perspective of electronic occupancies via Koopmans theorem, while ending with a further generalization of the Heisenberg observability and of its first application to mesosystems.
Abstract ................................................................................................. 164 3.1 Introduction .................................................................................. 165 3.2 The Wave-Function Continuity .................................................... 169 3.2.1 Quantum Tunneling and the Gamow Factor .................... 169 3.2.2 Nuclear Systems’ Lifetime by Alfa Disintegration .......... 176 3.3 Eigen-Energies and Eigen-Functions ........................................... 181 3.3.1 Atomic Hydrogenic States by Solving Laguerre Type Equations ................................................. 182 3.3.2 Molecular Vibrational States by Solving Hermite Type Equations .................................................. 200 3.3.3 Solid State Free Electronic States .................................... 209 3.4 Semiclassical Quantification of Energy ....................................... 216 3.4.1 Hydrogenic Atomic Systems ........................................... 219 3.4.2 Molecular Vibrational Systems ........................................ 222 3.4.3 Generalized |x|α Potential Systems ................................... 223 3.5 Variational Wave-Function and Energies ..................................... 228 3.5.1 Hydrogen’s Quantum Ground Level ................................ 228 3.5.2 Vibrational Ground Level ................................................ 231 3.5.3 Ground State Paradox of Free Electrons in Solids .......... 232 3.6 Causal Quantum Evolution .......................................................... 236 3.6.1 Schrödinger’s Picture ....................................................... 236 3.6.2 Unitary (“U”) Picture. Heisenberg Picture ...................... 246 3.6.3 Quantum Transitions: Interaction Picture ........................ 254 3.6.4 Green Function and Its Causal Properties ........................ 262 3.6.5 Free Particle’s Propagator ................................................ 271 3.7 Stationary Perturbations ............................................................... 274 3.7.1 General Perturbation Algorithm ....................................... 275 3.7.2 The Zeeman Effect ........................................................... 281 3.7.3 Nuclear Isotropic Corrections on Hydrogenic Atoms ...... 285 3.7.4 Harmonic Oscillator Perturbations .................................. 292 3.7.5 Quasi-Free Electronic Model of Solids ........................... 300 3.8 Quantum Measurements .............................................................. 304 3.8.1 Classical vs. Quantum Electric Resistance ...................... 306 3.8.2 Quantum Conservation Laws ............................................311 3.8.3 Quantum Elastic Scattering on Fixed Target ................... 318 3.8.4 More about Scattering: Born Approximation and Resonance Profile ..................................................... 332 3.8.5 From Yukawa Potential to Rutherford Scattering ............ 342 3.9 Conclusion ................................................................................... 353 Keywords .............................................................................................. 354 References ............................................................................................. 355 Author’s Main References ........................................................... 355 Specific References ...................................................................... 355 Further Readings .......................................................................... 355 ABSTRACT The phenomenological quantum mechanics is practically “re-storied” in a more formalized way, under the so-called extended quantum postulates, while opening and unfolding more complex analysis of the Nature’s phenomena, from nuclear, to atomic, to molecular, and to solid state and scattering observational quantum effects.
In the first part of this series we have shown how the Schrodinger equation for a single particle and the corresponding non relativistic quantum observables can be obtained from a purely classical phonon model through the Newtonian equations of motion. In this work we focus instead on how the classical Hamiltonian formalism applied to the same phonon system allows to recover the feature of relativistic quantum mechanics for a single spinless particle. Using the classical nature of the phonon model, we naturally define continuous Poisson brackets between classical observables, which allows to recover the dynamics of such observables, i.e. the Ehrenfest relations associated to real-valued Klein-Gordon fields. The Poisson brackets also permits to obtain the generic form of constants of motions, thus generalizing the concept of inner products and momentum on Klein-Gordon fields. We then connect the formalism of real-valued classical functionals with that of hermitian operators and complex-valued wave functions. This is done through the introduction of a non-local complex-valued change of variables which allows to rewrite the real-valued Klein-Gordon equation in a form akin to the Schrodinger equation, and the classical observables as quantum expectation values. Then, we show how this change of variables allows to rewrite the classical Poisson brackets as commutators of hermitian operators. This points out the strict equivalence between the Heisenberg formalism and the formalism of classical Poisson bracket. Eventually, we illustrate how the Poisson brackets allows to recover the transformations of Poincare group in 1+1 dimension together with its algebra. The latter makes the link between the Lorentz invariant inner product of Mostafazadeh and the Casimir invariant associated to the mass of particle.
Abstract Chapter 1 opens with a brief review of some basic features of quantum mechanics, including the Schrödinger equation, linear and angular momentum and the theory of the hydrogenic atom: It also includes complete orthonormal sets of eigenfunctions, the translation operator, current, spin, equation of continuity, gauge transformation, determinant & permanent multiparticle energy eigenfunctions for noninteracting particles and the Pauli exclusion principle. Attention is then focused on Dirac bra-ket notation and complete sets of commuting observables. In this connection, representations and transformation among representations are discussed in detail for the Schrödinger system state vector and the eigenstates, as well as bra-ket matrix elements of operators. Finally, Schwinger’s interpretation of ket-bra matrix operator structures (Schwinger “Measurement Symbols”) in terms of annihilation and creation of systems in eigenstates is introduced.