An attempt is made to refine the classical concept of molecular structure in the light of quantum theory. It is argued that a definite molecular structure can only be associated with quantum states that are intrinsically time-dependent and therefore need not manifest the full symmetry implied by the relativity principle; conversely if a molecule is definitely observed in an eigenstate of its associated molecular Schrödinger equation, a molecular structure description is inappropriate. The theme of the article is illustrated with examples drawn from spectroscopy, dielectric phenomena, electron scattering, stereoisomerism and optical activity.
An attempt is made to refine the classical concept of molecular structure in the light of quantum theory. It is argued that a definite molecular structure can only be associated with quantum states that are intrinsically time-dependent and therefore need not manifest the full symmetry implied by the relativity principle; conversely if a molecule is definitely observed in an eigenstate of its associated molecular Schrödinger equation, a molecular structure description is inappropriate. The theme of the article is illustrated with examples drawn from spectroscopy, dielectric phenomena, electron scattering, stereoisomerism and optical activity.
Abstract The classical concept of molecular structure (namely, a set of atoms with a well‐defined geometrical arrangement in space) originated well before the advent of quantum theory, and, contrary to widespread views, these two conceptual schemes (classical molecular structure and quantum theory) are not easy to reconcile. We begin with a preliminary discussion of molecular structure in terms of space and time correlations in the framework of quantum theory. Then we summarize the salient features of some critical views raised‐during recent years (essentially by Woolley) concerning the concept of molecular structure. The essential claim of this viewpoint is that “molecular structure” is not an intrinsic attribute of an isolated molecule, and appears rather as an effect of the environment (other molecules? vacuum electromagnetic field, according to quantum electrodynamics?). Afterwards, we discuss these issues in detail: we show that it is necessary to distinguish between a “quantum” or “potential” structure (which may be deduced in a straightforward way from the quantum treatment of the molecule), and the “classical” molecular structure (according to which the molecule is considered as a set of rotating and vibrating material points, corresponding to the atoms); we briefly discuss some aspects of the Born–Oppenheimer approximation. From our discussion, we deduce that the “classical structure” concept is indeed non‐trivial from a purely quantum‐mechanical point of view; in actual fact, it is related to the problem of the “classical limit” of quantum mechanics, and it appears that, at the present time, none of these classical concepts and behaviours is convincingly derivable from a strict quantum mechanical basis. Finally, we consider these same problems from the point of view of stochastic electrodynamics (SED), which is one of the stochastic models for microphysics proposed so far as a possible alternative or extension of usual quantum theory. In the framework of such a theory, the “classical limit” and, in particular, the “classical molecular structure” no longer poses a problem, but aside from these satisfactory qualitative aspects, several quantitative failures of SED prevent us from accepting it, at least in its present state, as a genuine physical alternative to quantum theory. We therefore conclude that “classical molecular structure”, and classical concepts in general, remain an open problem in the framework of present‐day quantum physics.
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.
CHAPTER 1: FROM CLASSICAL TO QUANTUM MECHANICS 1.1 Why Study Quantum Mechanics? 1.2 Quantum Mechanics Arose Out of the Interplay of Experiments and Theory 1.3 Blackbody Radiation 1.4 The Photoelectric Effect 1.5 Particles Exhibit Wave-Like Behavior 1.6 Diffraction by a Double Slit 1.7 Atomic Spectra and the Bohr Model for the Hydrogen Atom CHAPTER 2: THE SCHRODINGER EQUATION 2.1 What Determines If a System Needs to Be Described Using Quantum Mechanics? 2.2 Classical Waves and the Nondispersive Wave Equation 2.3 Waves Are Conveniently Represented as Complex Functions 2.4 Quantum Mechanical Waves and the Schrodinger Equation 2.5 Solving the Schrodinger Equation: Operators, Observables, Eigenfunctions, and Eigenvalues 2.6 The Eigenfunctions of a Quantum Mechanical Operator Are Orthogonal 2.7 The Eigenfunctions of a Quantum Mechanical Operator Form a Complete Set 2.8 Summing Up the New Concepts CHAPTER 3: THE QUANTUM MECHANICAL POSTULATES 3.1 The Physical Meaning Associated with the Wave Function 3.2 Every Observable Has a Corresponding Operator 3.3 The Result of an Individual Measurement 3.4 The Expectation Value 3.5 The Evolution in Time of a Quantum Mechanical System CHAPTER 4: USING QUANTUM MECHANICS ON SIMPLE SYSTEMS 4.1 The Free Particle 4.2 The Particle in a One-Dimensional Box 4.3 Two- and Three-Dimensional Boxes 4.4 Using the Postulates to Understand the Particle in the Box and Vice Versa CHAPTER 5: THE PARTICLE IN THE BOX AND THE REAL WORLD 5.1 The Particle in the Finite Depth Box 5.2 Differences in Overlap between Core and Valence Electrons 5.3 Pi Electrons in Conjugated Molecules Can Be Treated as Moving Freely in a Box 5.4 Why Does Sodium Conduct Electricity and Why Is Diamond an Insulator? 5.5 Tunneling through a Barrier 5.6 The Scanning Tunneling Microscope 5.7 Tunneling in Chemical Reactions 5.8 (Supplemental) Quantum Wells and Quantum Dots CHAPTER 6: COMMUTING AND NONCOMMUTING OPERATORS AND THE SURPRISING CONSEQUENCES OF ENTANGLEMENT 6.1 Commutation Relations 6.2 The Stern-Gerlach Experiment 6.3 The Heisenberg Uncertainty Principle 6.4 (Supplemental) The Heisenberg Uncertainty Principle Expressed in Terms of Standard Deviations 6.5 (Supplemental) A Thought Experiment Using a Particle in a Three-Dimensional Box 6.6 (Supplemental) Entangled States, Teleportation, and Quantum Computers CHAPTER 7: A QUANTUM MECHANICAL MODEL FOR THE VIBRATION AND ROTATION OF MOLECULES 7.1 Solving the Schrodinger Equation for the Quantum Mechanical Harmonic Oscillator 7.2 Solving the Schrodinger Equation for Rotation in Two Dimensions 7.3 Solving the Schrodinger Equation for Rotation in Three Dimensions 7.4 The Quantization of Angular Momentum 7.5 The Spherical Harmonic Functions 7.6 (Optional Review) The Classical Harmonic Oscillator 7.7 (Optional Review) Angular Motion and the Classical Rigid Rotor 7.8 (Supplemental) Spatial Quantization CHAPTER 8: THE VIBRATIONAL AND ROTATIONAL SPECTROSCOPY OF DIATOMIC MOLECULES 8.1 An Introduction to Spectroscopy 8.2 Absorption, Spontaneous Emission, and Stimulated Emission 8.3 An Introduction to Vibrational Spectroscopy 8.4 The Origin of Selection Rules 8.5 Infrared Absorption Spectroscopy 8.6 Rotational Spectroscopy 8.7 (Supplemental) Fourier Transform Infrared Spectroscopy 8.8 (Supplemental) Raman Spectroscopy 8.9 (Supplemental) How Does the Transition Rate between States Depend on Frequency? CHAPTER 9: THE HYDROGEN ATOM 9.1 Formulating the Schrodinger Equation 9.2 Solving the Schrodinger Equation for the Hydrogen Atom 9.3 Eigenvalues and Eigenfunctions for the Total Energy 9.4 The Hydrogen Atom Orbitals 9.5 The Radial Probability Distribution Function 9.6 The Validity of the Shell Model of an Atom CHAPTER 10: MANY-ELECTRON ATOMS 10.1 Helium: The Smallest Many-Electron Atom 10.2 Introducing Electron Spin 10.3 Wave Functions Must Reflect the Indistinguishability of Electrons 10.4 Using the Variational Method to Solve the Schrodinger Equation 10.5 The Hartree-Fock Self-Consistent Field Method 10.6 Understanding Trends in the Periodic Table from Hartree-Fock Calculations CHAPTER 11: QUANTUM STATES FOR MANY-ELECTRON ATOMS AND ATOMIC SPECTROSCOPY 11.1 Good Quantum Numbers, Terms, Levels, and States 11.2 The Energy of a Configuration Depends on Both Orbital and Spin Angular Momentum 11.3 Spin-Orbit Coupling Breaks Up a Term into Levels 11.4 The Essentials of Atomic Spectroscopy 11.5 Analytical Techniques Based on Atomic Spectroscopy 11.6 The Doppler Effect 11.7 The Helium-Neon Laser 11.8 Laser Isotope Separation 11.9 Auger Electron and X-Ray Photoelectron Spectroscopies 11.10 Selective Chemistry of Excited States: O(3P) and O(1D) 11.11 (Supplemental) Configurations with Paired and Unpaired Electron Spins Differ in Energy CHAPTER 12: THE CHEMICAL BOND IN DIATOMIC MOLECULES 12.1 The Simplest One-Electron Molecule: 12.2 The Molecular Wave Function for Ground-State 12.3 The Energy Corresponding to the H2+ Molecular Wave Functions 12.4 A Closer Look at the H2+ Molecular Wave Functions 12.5 Combining Atomic Orbitals to Form Molecular Orbitals 12.6 Molecular Orbitals for Homonuclear Diatomic Molecules 12.7 The Electronic Structure of Many-Electron Molecules 12.8 Bond Order, Bond Energy, and Bond Length 12.9 Heteronuclear Diatomic Molecules 12.10 The Molecular Electrostatic Potential CHAPTER 13: MOLECULAR STRUCTURE AND ENERGY LEVELS FOR POLYATOMIC MOLECULES 13.1 Lewis Structures and the VSEPR Model 13.2 Describing Localized Bonds Using Hybridization for Methane, Ethene, and Ethyne 13.3 Constructing Hybrid Orbitals for Nonequivalent Ligands 13.4 Using Hybridization to Describe Chemical Bonding 13.5 Predicting Molecular Structure Using Molecular Orbital Theory 13.6 How Different Are Localized and Delocalized Bonding Models? 13.7 Qualitative Molecular Orbital Theory for Conjugated and Aromatic Molecules: The Huckel Model 13.8 From Molecules to Solids 13.9 Making Semiconductors Conductive at Room Temperature CHAPTER 14: ELECTRONIC SPECTROSCOPY 14.1 The Energy of Electronic Transitions 14.2 Molecular Term Symbols 14.3 Transitions between Electronic States of Diatomic Molecules 14.4 The Vibrational Fine Structure of Electronic Transitions in Diatomic Molecules 14.5 UV-Visible Light Absorption in Polyatomic Molecules 14.6 Transitions among the Ground and Excited States 14.7 Singlet--Singlet Transitions: Absorption and Fluorescence 14.8 Intersystem Crossing and Phosphorescence 14.9 Fluorescence Spectroscopy and Analytical Chemistry 14.10 Ultraviolet Photoelectron Spectroscopy 14.11 Single Molecule Spectroscopy 14.12 Fluorescent Resonance Energy Transfer (FRET) 14.13 Linear and Circular Dichroism 14.14 (Supplemental) Assigning + and -- to Terms of Diatomic Molecules CHAPTER 15: COMPUTATIONAL CHEMISTRY 15.1 The Promise of Computational Chemistry 15.2 Potential Energy Surfaces 15.3 Hartree-Fock Molecular Orbital Theory: A Direct Descendant of the Schrodinger Equation 15.4 Properties of Limiting Hartree-Fock Models 15.5 Theoretical Models and Theoretical Model Chemistry 15.6 Moving Beyond Hartree-Fock Theory 15.7 Gaussian Basis Sets 15.8 Selection of a Theoretical Model 15.9 Graphical Models 15.10 Conclusion CHAPTER 16: MOLECULAR SYMMETRY 16.1 Symmetry Elements, Symmetry Operations, and Point Groups 16.2 Assigning Molecules to Point Groups 16.3 The H2O Molecule and the C2v Point Group 16.4 Representations of Symmetry Operators, Bases for Representations, and the Character Table 16.5 The Dimension of a Representation 16.6 Using the C2v Representations to Construct Molecular Orbitals for H2O 16.7 The Symmetries of the Normal Modes of Vibration of Molecules 16.8 Selection Rules and Infrared versus Raman Activity 16.9 (Supplemental) Using the Projection Operator Method to Generate MOs That Are Bases for Irreducible Representations CHAPTER 17: NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 17.1 Intrinsic Nuclear Angular Momentum and Magnetic Moment 17.2 The Energy of Nuclei of Nonzero Nuclear Spin in a Magnetic Field 17.3 The Chemical Shift for an Isolated Atom 17.4 The Chemical Shift for an Atom Embedded in a Molecule 17.5 Electronegativity of Neighboring Groups and Chemical Shifts 17.6 Magnetic Fields of Neighboring Groups and Chemical Shifts 17.7 Multiplet Splitting of NMR Peaks Arises through Spin--Spin Coupling 17.8 Multiplet Splitting When More Than Two Spins Interact 17.9 Peak Widths in NMR Spectroscopy 17.10 Solid-State NMR 17.11 NMR Imaging 17.12 (Supplemental) The NMR Experiment in the Laboratory and Rotating Frames 17.13 (Supplemental) Fourier Transform NMR Spectroscopy 17.14 (Supplemental) Two-Dimensional NMR
The prevailing interpretation of quantum mechanics, often referred to as the Copenhagen interpretation, posits a fundamental disturbance caused by measurement, collapsing the wave function and defining a definite state. This theory, termed the Molecular Reality Reconstruction Theory (MRRT), offers an alternative perspective. It argues that the observed measurement outcome represents a reconstructed reality, rather than a direct reflection of the initial, underlying molecular state. The theory proposes a framework for identifying the true, pre-measurement molecular state, drawing parallels with the quantum measurement problem. We explore the concept of a "hidden variable" associated with each molecule, suggesting that the measured outcome is a projection of this hidden variable onto a specific observable, rather than a fundamental alteration of the molecule itself. This reconstruction process is inherently probabilistic, governed by the underlying quantum mechanical framework. The central tenet of MRRT is that the observed molecular state is a consequence of this reconstruction process, and not a direct manifestation of the molecule's intrinsic properties before measurement. This framework seeks to resolve the inherent paradoxes associated with the collapse of the wave function and provides a new lens through which to understand the relationship between measurement and reality. The theory's foundation rests on the idea that the act of measurement interacts with the molecule to produce the observed result, rather than the molecule directly determining the outcome. Mathematical formalism is presented to illustrate the core concepts and relationships within this theory.
Whether or not quantum physics can account for molecular structure is a matter of considerable controversy. Three of the problems raised in this regard are the problems of molecular structure. We argue that these problems are just special cases of the measurement problem of quantum mechanics: insofar as the measurement problem is solved, the problems of molecular structure are resolved as well. In addition, we explore one consequence of our argument: that claims about the reduction or emergence of molecular structure cannot be settled independently of the choice of a particular resolution to the measurement problem. Specifically, we consider how three standard putative solutions to the measurement problem inform our understanding of a molecule in isolation, as well as of chemistry’s relation to quantum physics.
With the advent of general relativity and quantum mechanics, physics has in many cases shifted the emphasis from dynamics to symmetry principles associated with different types of mathematical groups. We speak of the group structure of crystals, the group invariants of the equations of motion, the group classification of elementary particles, and also of the group homeomorphisms of fractals. The objective of this article is to show how the group theoretical structure of entanglement can be used to classify atomic and molecular structure. The article begins by establishing a working definition of entanglement and then using it to derive the Pauli-exclusion principle by showing that Fermi-Dirac statistics can be considered as an entangled state invariant under the action of the SL(n, C)With the advent of general relativity and quantum mechanics, physics has in many cases shifted the emphasis from dynamics to symmetry principles associated with different types of mathematical groups. We speak of the group structure of crystals, the group invariants of the equations of motion, the group classification of elementary particles, and also of the group homeomorphisms of fractals. The objective of this article is to show how the group theoretical structure of entanglement can be used to classify atomic and molecular structure. The article begins by establishing a working definition of entanglement and then using it to derive the Pauli-exclusion principle by showing that Fermi-Dirac statistics can be considered as an entangled state invariant under the action of the SL(n,C) group. Based on this, a group classification scheme of entangled states is proposed to distinguish atomic and molecular structures associated with chemical bonds. group. Based on this, a group classification scheme of entangled states is proposed to distinguish atomic and molecular structures associated with chemical bonds.