Force field (chemistry)

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Force_field_(chemistry)

Part of force field of ethane for the C-C stretching bond.

In the context of chemistry, molecular physics, physical chemistry, and molecular modelling, a force field is a computational model that is used to describe the forces between atoms (or collections of atoms) within molecules or between molecules as well as in crystals. Force fields are a variety of interatomic potentials. More precisely, the force field refers to the functional form and parameter sets used to calculate the potential energy of a system on the atomistic level. Force fields are usually used in molecular dynamics or Monte Carlo simulations. The parameters for a chosen energy function may be derived from classical laboratory experiment data, calculations in quantum mechanics, or both. Force fields utilize the same concept as force fields in classical physics, with the main difference being that the force field parameters in chemistry describe the energy landscape on the atomistic level. From a force field, the acting forces on every particle are derived as a gradient of the potential energy with respect to the particle coordinates.

A large number of different force field types exist today (e.g. for organic molecules, ions, polymers, minerals, and metals). Depending on the material, different functional forms are usually chosen for the force fields since different types of atomistic interactions dominate the material behavior.

There are various criteria that can be used for categorizing force field parametrization strategies. An important differentiation is 'component-specific' and 'transferable'. For a component-specific parametrization, the considered force field is developed solely for describing a single given substance (e.g. water). For a transferable force field, all or some parameters are designed as building blocks and become transferable/ applicable for different substances (e.g. methyl groups in alkane transferable force fields). A different important differentiation addresses the physical structure of the models: All-atom force fields provide parameters for every type of atom in a system, including hydrogen, while united-atom interatomic potentials treat the hydrogen and carbon atoms in methyl groups and methylene bridges as one interaction center. Coarse-grained potentials, which are often used in long-time simulations of macromolecules such as proteins, nucleic acids, and multi-component complexes, sacrifice chemical details for higher computing efficiency.

Force fields for molecular systems

Molecular mechanics potential energy function with continuum solvent.

The basic functional form of potential energy for modeling molecular systems includes intramolecular interaction terms for interactions of atoms that are linked by covalent bonds, and intermolecular (i.e. nonbonded also termed noncovalent) terms that describe the long-range electrostatic and van der Waals forces. The specific decomposition of the terms depends on the force field, but a general form for the total energy in an additive force field can be written as $${\displaystyle E_{\text{total}}=E_{\text{bonded}}+E_{\text{nonbonded}}}$$ where the components of the covalent and noncovalent contributions are given by the following summations: $${\displaystyle E_{\text{bonded}}=E_{\text{bond}}+E_{\text{angle}}+E_{\text{dihedral}}}$$ $${\displaystyle E_{\text{nonbonded}}=E_{\text{electrostatic}}+E_{\text{van der Waals}}}$$

The bond and angle terms are usually modeled by quadratic energy functions that do not allow bond breaking. A more realistic description of a covalent bond at higher stretching is provided by the more expensive Morse potential. The functional form for dihedral energy is variable from one force field to another. Additionally, "improper torsional" terms may be added to enforce the planarity of aromatic rings and other conjugated systems, and "cross-terms" that describe the coupling of different internal variables, such as angles and bond lengths. Some force fields also include explicit terms for hydrogen bonds.

The nonbonded terms are computationally most intensive. A popular choice is to limit interactions to pairwise energies. The van der Waals term is usually computed with a Lennard-Jones potential or the Mie potential and the electrostatic term with Coulomb's law. However, both can be buffered or scaled by a constant factor to account for electronic polarizability. A large number of force fields based on this or similar energy expressions have been proposed in the past decades for modeling different types of materials such as molecular substances, metals, glasses etc. - see below for a comprehensive list of force fields.

Bond stretching

As it is rare for bonds to deviate significantly from their equilibrium values, the most simplistic approaches utilize a Hooke's law formula: $${\displaystyle E_{\text{bond}}=\frac{k_{ij}}{2}(l_{ij}-l_{0,ij}{)}^2,}$$ where ${\displaystyle k_{ij}}$ is the force constant, ${\displaystyle l_{ij}}$ is the bond length, and ${\displaystyle l_{0,ij}}$ is the value for the bond length between atoms ${\displaystyle i}$ and ${\displaystyle j}$ when all other terms in the force field are set to 0. The term ${\displaystyle l_{0,ij}}$ is at times differently defined or taken at different thermodynamic conditions.

The bond stretching constant ${\displaystyle k_{ij}}$ can be determined from the experimental infrared spectrum, Raman spectrum, or high-level quantum-mechanical calculations. The constant ${\displaystyle k_{ij}}$ determines vibrational frequencies in molecular dynamics simulations. The stronger the bond is between atoms, the higher is the value of the force constant, and the higher the wavenumber (energy) in the IR/Raman spectrum.

Though the formula of Hooke's law provides a reasonable level of accuracy at bond lengths near the equilibrium distance, it is less accurate as one moves away. In order to model the Morse curve better, one could employ cubic and higher powers. However, for most practical applications these differences are negligible, and inaccuracies in predictions of bond lengths are on the order of the thousandth of an angstrom, which is also the limit of reliability for common force fields. A Morse potential can be employed instead to enable bond breaking and higher accuracy, even though it is less efficient to compute. For reactive force fields, bond breaking and bond orders are additionally considered.

Electrostatic interactions

Electrostatic interactions are represented by a Coulomb energy, which utilizes atomic charges ${\displaystyle q_i}$ to represent chemical bonding ranging from covalent to polar covalent and ionic bonding. The typical formula is the Coulomb law: $${\displaystyle E_{\text{Coulomb}}=\frac{1}{4\pi {\epsilon }_0}\frac{q_i{q}_j}{r_{ij}},}$$ where ${\displaystyle r_{ij}}$ is the distance between two atoms ${\displaystyle i}$ and ${\displaystyle j}$. The total Coulomb energy is a sum over all pairwise combinations of atoms and usually excludes 1, 2 bonded atoms, 1, 3 bonded atoms, as well as 1, 4 bonded atoms.

Atomic charges can make dominant contributions to the potential energy, especially for polar molecules and ionic compounds, and are critical to simulate the geometry, interaction energy, and the reactivity. The assignment of charges usually uses some heuristic approach, with different possible solutions.

Force fields for crystal systems

Atomistic interactions in crystal systems significantly deviate from those in molecular systems, e.g. of organic molecules. For crystal systems, particularly multi-body interactions, these interactions are important and cannot be neglected if a high accuracy of the force field is the aim. For crystal systems with covalent bonding, bond order potentials are usually used, e.g. Tersoff potentials. For metal systems, usually embedded atom potentials are used. Additionally, Drude model potentials have been developed, which describe a form of attachment of electrons to nuclei.

Parameterization

In addition to the functional form of the potentials, a force fields consists of the parameters of these functions. Together, they specify the interactions on the atomistic level. The parametrization, i.e. determining of the parameter values, is crucial for the accuracy and reliability of the force field. Different parametrization procedures have been developed for the parametrization of different substances, e.g. metals, ions, and molecules. For different material types, usually different parametrization strategies are used. In general, two main types can be distinguished for the parametrization, either using data/ information from the atomistic level, e.g. from quantum mechanical calculations or spectroscopic data, or using data from macroscopic properties, e.g. the hardness or compressibility of a given material. Often a combination of these routes is used. Hence, one way or the other, the force field parameters are always determined in an empirical way. Nevertheless, the term 'empirical' is often used in the context of force field parameters when macroscopic material property data was used for the fitting. Experimental data (microscopic and macroscopic) included for the fit, for example, the enthalpy of vaporization, enthalpy of sublimation, dipole moments, and various spectroscopic properties such as vibrational frequencies. Often, for molecular systems, quantum mechanical calculations in the gas phase are used for parametrizing intramolecular interactions and parametrizing intermolecular dispersive interactions by using macroscopic properties such as liquid densities. The assignment of atomic charges often follows quantum mechanical protocols with some heuristics, which can lead to significant deviation in representing specific properties.

A large number of workflows and parametrization procedures have been employed in the past decades using different data and optimization strategies for determining the force field parameters. They differ significantly, which is also due to different focuses of different developments. The parameters for molecular simulations of biological macromolecules such as proteins, DNA, and RNA were often derived/transferred from observations for small organic molecules, which are more accessible for experimental studies and quantum calculations.

Atom types are defined for different elements as well as for the same elements in sufficiently different chemical environments. For example, oxygen atoms in water and an oxygen atoms in a carbonyl functional group are classified as different force field types. Typical molecular force field parameter sets include values for atomic mass, atomic charge, Lennard-Jones parameters for every atom type, as well as equilibrium values of bond lengths, bond angles, and dihedral angles. The bonded terms refer to pairs, triplets, and quadruplets of bonded atoms, and include values for the effective spring constant for each potential.

Heuristic force field parametrization procedures have been very successful for many years, but recently criticized since they are usually not fully automated and therefore subject to some subjectivity of the developers, which also brings problems regarding the reproducibility of the parametrization procedure.

Efforts to provide open source codes and methods include openMM and openMD. The use of semi-automation or full automation, without input from chemical knowledge, is likely to increase inconsistencies at the level of atomic charges, for the assignment of remaining parameters, and likely to dilute the interpretability and performance of parameters.

Force field databases

A large number of force fields has been published in the past decades - mostly in scientific publications. In recent years, some databases have attempted to collect, categorize and make force fields digitally available. Therein, different databases focus on different types of force fields. For example, the openKim database focuses on interatomic functions describing the individual interactions between specific elements. The TraPPE database focuses on transferable force fields of organic molecules (developed by the Siepmann group). The MolMod database focuses on molecular and ionic force fields (both component-specific and transferable).

Transferability and mixing function types

Functional forms and parameter sets have been defined by the developers of interatomic potentials and feature variable degrees of self-consistency and transferability. When functional forms of the potential terms vary or are mixed, the parameters from one interatomic potential function can typically not be used together with another interatomic potential function. In some cases, modifications can be made with minor effort, for example, between 9-6 Lennard-Jones potentials to 12-6 Lennard-Jones potentials. Transfers from Buckingham potentials to harmonic potentials, or from Embedded Atom Models to harmonic potentials, on the contrary, would require many additional assumptions and may not be possible.

In many cases, force fields can be straight forwardly combined. Yet, often, additional specifications and assumptions are required.

Limitations

All interatomic potentials are based on approximations and experimental data, therefore often termed empirical. The performance varies from higher accuracy than density functional theory (DFT) calculations, with access to million times larger systems and time scales, to random guesses depending on the force field. The use of accurate representations of chemical bonding, combined with reproducible experimental data and validation, can lead to lasting interatomic potentials of high quality with much fewer parameters and assumptions in comparison to DFT-level quantum methods.

Possible limitations include atomic charges, also called point charges. Most force fields rely on point charges to reproduce the electrostatic potential around molecules, which works less well for anisotropic charge distributions. The remedy is that point charges have a clear interpretation and virtual electrons can be added to capture essential features of the electronic structure, such additional polarizability in metallic systems to describe the image potential, internal multipole moments in π-conjugated systems, and lone pairs in water. Electronic polarization of the environment may be better included by using polarizable force fields or using a macroscopic dielectric constant. However, application of one value of dielectric constant is a coarse approximation in the highly heterogeneous environments of proteins, biological membranes, minerals, or electrolytes.

All types of van der Waals forces are also strongly environment-dependent because these forces originate from interactions of induced and "instantaneous" dipoles (see Intermolecular force). The original Fritz London theory of these forces applies only in a vacuum. A more general theory of van der Waals forces in condensed media was developed by A. D. McLachlan in 1963 and included the original London's approach as a special case. The McLachlan theory predicts that van der Waals attractions in media are weaker than in vacuum and follow the like dissolves like rule, which means that different types of atoms interact more weakly than identical types of atoms. This is in contrast to combinatorial rules or Slater-Kirkwood equation applied for development of the classical force fields. The combinatorial rules state that the interaction energy of two dissimilar atoms (e.g., C...N) is an average of the interaction energies of corresponding identical atom pairs (i.e., C...C and N...N). According to McLachlan's theory, the interactions of particles in media can even be fully repulsive, as observed for liquid helium, however, the lack of vaporization and presence of a freezing point contradicts a theory of purely repulsive interactions. Measurements of attractive forces between different materials (Hamaker constant) have been explained by Jacob Israelachvili. For example, "the interaction between hydrocarbons across water is about 10% of that across vacuum". Such effects are represented in molecular dynamics through pairwise interactions that are spatially more dense in the condensed phase relative to the gas phase and reproduced once the parameters for all phases are validated to reproduce chemical bonding, density, and cohesive/surface energy.

Limitations have been strongly felt in protein structure refinement. The major underlying challenge is the huge conformation space of polymeric molecules, which grows beyond current computational feasibility when containing more than ~20 monomers. Participants in Critical Assessment of protein Structure Prediction (CASP) did not try to refine their models to avoid "a central embarrassment of molecular mechanics, namely that energy minimization or molecular dynamics generally leads to a model that is less like the experimental structure". Force fields have been applied successfully for protein structure refinement in different X-ray crystallography and NMR spectroscopy applications, especially using program XPLOR. However, the refinement is driven mainly by a set of experimental constraints and the interatomic potentials serve mainly to remove interatomic hindrances. The results of calculations were practically the same with rigid sphere potentials implemented in program DYANA (calculations from NMR data), or with programs for crystallographic refinement that use no energy functions at all. These shortcomings are related to interatomic potentials and to the inability to sample the conformation space of large molecules effectively. Thereby also the development of parameters to tackle such large-scale problems requires new approaches. A specific problem area is homology modeling of proteins. Meanwhile, alternative empirical scoring functions have been developed for ligand docking, protein folding, homology model refinement, computational protein design, and modeling of proteins in membranes.

It was also argued that some protein force fields operate with energies that are irrelevant to protein folding or ligand binding. The parameters of proteins force fields reproduce the enthalpy of sublimation, i.e., energy of evaporation of molecular crystals. However, protein folding and ligand binding are thermodynamically closer to crystallization, or liquid-solid transitions as these processes represent freezing of mobile molecules in condensed media. Thus, free energy changes during protein folding or ligand binding are expected to represent a combination of an energy similar to heat of fusion (energy absorbed during melting of molecular crystals), a conformational entropy contribution, and solvation free energy. The heat of fusion is significantly smaller than enthalpy of sublimation. Hence, the potentials describing protein folding or ligand binding need more consistent parameterization protocols, e.g., as described for IFF. Indeed, the energies of H-bonds in proteins are ~ -1.5 kcal/mol when estimated from protein engineering or alpha helix to coil transition data, but the same energies estimated from sublimation enthalpy of molecular crystals were -4 to -6 kcal/mol, which is related to re-forming existing hydrogen bonds and not forming hydrogen bonds from scratch. The depths of modified Lennard-Jones potentials derived from protein engineering data were also smaller than in typical potential parameters and followed the like dissolves like rule, as predicted by McLachlan theory.

Force fields available in literature

Further information: Comparison of force field implementations, Molecular design software, and Comparison of software for molecular mechanics modeling

Different force fields are designed for different purposes:

Classical

• AMBER (Assisted Model Building and Energy Refinement) – widely used for proteins and DNA.
• CFF (Consistent Force Field) – a family of force fields adapted to a broad variety of organic compounds, includes force fields for polymers, metals, etc. CFF was developed by Arieh Warshel, Lifson, and coworkers as a general method for unifying studies of energies, structures, and vibration of general molecules and molecular crystals. The CFF program, developed by Levitt and Warshel, is based on the Cartesian representation of all the atoms, and it served as the basis for many subsequent simulation programs.
• CHARMM (Chemistry at HARvard Molecular Mechanics) – originally developed at Harvard, widely used for both small molecules and macromolecules
• COSMOS-NMR – hybrid QM/MM force field adapted to various inorganic compounds, organic compounds, and biological macromolecules, including semi-empirical calculation of atomic charges NMR properties. COSMOS-NMR is optimized for NMR-based structure elucidation and implemented in COSMOS molecular modelling package.
• CVFF – also used broadly for small molecules and macromolecules.
• ECEPP – first force field for polypeptide molecules - developed by F.A. Momany, H.A. Scheraga and colleagues. ECEPP was developed specifically for the modeling of peptides and proteins. It uses fixed geometries of amino acid residues to simplify the potential energy surface. Thus, the energy minimization is conducted in the space of protein torsion angles. Both MM2 and ECEPP include potentials for H-bonds and torsion potentials for describing rotations around single bonds. ECEPP/3 was implemented (with some modifications) in Internal Coordinate Mechanics and FANTOM.
• GROMOS (GROningen MOlecular Simulation) – a force field that comes as part of the GROMOS software, a general-purpose molecular dynamics computer simulation package for the study of biomolecular systems. GROMOS force field A-version has been developed for application to aqueous or apolar solutions of proteins, nucleotides, and sugars. A B-version to simulate gas phase isolated molecules is also available.
• IFF (Interface Force Field) – covers metals, minerals, 2D materials, and polymers. It uses 12-6 LJ and 9-6 LJ interactions. IFF was developed as for compounds across the periodic table. It assigs consistent charges, utilizes standard conditions as a reference state, reproduces structures, energies, and energy derivatives, and quantifies limitations for all included compounds. The Interface force field (IFF) assumes one single energy expression for all compounds across the periodic (with 9-6 and 12-6 LJ options). The IFF is in most parts non-polarizable, but also comprises polarizable parts, e.g. for some metals (Au, W) and pi-conjugated molecules
• MMFF (Merck Molecular Force Field) – developed at Merck for a broad range of molecules.
• MM2 was developed by Norman Allinger mainly for conformational analysis of hydrocarbons and other small organic molecules. It is designed to reproduce the equilibrium covalent geometry of molecules as precisely as possible. It implements a large set of parameters that is continuously refined and updated for many different classes of organic compounds (MM3 and MM4).
• OPLS (Optimized Potential for Liquid Simulations) (variants include OPLS-AA, OPLS-UA, OPLS-2001, OPLS-2005, OPLS3e, OPLS4) – developed by William L. Jorgensen at the Yale University Department of Chemistry.
• QCFF/PI – A general force fields for conjugated molecules.
• UFF (Universal Force Field) – A general force field with parameters for the full periodic table up to and including the actinoids, developed at Colorado State University. The reliability is known to be poor due to lack of validation and interpretation of the parameters for nearly all claimed compounds, especially metals and inorganic compounds.

Polarizable

Several force fields explicitly capture polarizability, where a particle's effective charge can be influenced by electrostatic interactions with its neighbors. Core-shell models are common, which consist of a positively charged core particle, representing the polarizable atom, and a negatively charged particle attached to the core atom through a spring-like harmonic oscillator potential. Recent examples include polarizable models with virtual electrons that reproduce image charges in metals and polarizable biomolecular force fields.

• AMBER – polarizable force field developed by Jim Caldwell and coworkers.
• AMOEBA (Atomic Multipole Optimized Energetics for Biomolecular Applications) – force field developed by Pengyu Ren (University of Texas at Austin) and Jay W. Ponder (Washington University). AMOEBA force field is gradually moving to more physics-rich AMOEBA+.
• CHARMM – polarizable force field developed by S. Patel (University of Delaware) and C. L. Brooks III (University of Michigan). Based on the classical Drude oscillator developed by Alexander MacKerell (University of Maryland, Baltimore) and Benoit Roux (University of Chicago).
• CFF/ind and ENZYMIX – The first polarizable force field which has subsequently been used in many applications to biological systems.
• COSMOS-NMR (Computer Simulation of Molecular Structure) – developed by Ulrich Sternberg and coworkers. Hybrid QM/MM force field enables explicit quantum-mechanical calculation of electrostatic properties using localized bond orbitals with fast BPT formalism. Atomic charge fluctuation is possible in each molecular dynamics step.
• DRF90 – developed by P. Th. van Duijnen and coworkers.
• NEMO (Non-Empirical Molecular Orbital) – procedure developed by Gunnar Karlström and coworkers at Lund University (Sweden)
• PIPF – The polarizable intermolecular potential for fluids is an induced point-dipole force field for organic liquids and biopolymers. The molecular polarization is based on Thole's interacting dipole (TID) model and was developed by Jiali Gao Gao Research Group | at the University of Minnesota.
• Polarizable Force Field (PFF) – developed by Richard A. Friesner and coworkers.
• SP-basis Chemical Potential Equalization (CPE) – approach developed by R. Chelli and P. Procacci.
• PHAST – polarizable potential developed by Chris Cioce and coworkers.
• ORIENT – procedure developed by Anthony J. Stone (Cambridge University) and coworkers.
• Gaussian Electrostatic Model (GEM) – a polarizable force field based on Density Fitting developed by Thomas A. Darden and G. Andrés Cisneros at NIEHS; and Jean-Philip Piquemal at Paris VI University.
• Atomistic Polarizable Potential for Liquids, Electrolytes, and Polymers(APPLE&P), developed by Oleg Borogin, Dmitry Bedrov and coworkers, which is distributed by Wasatch Molecular Incorporated.
• Polarizable procedure based on the Kim-Gordon approach developed by Jürg Hutter and coworkers (University of Zürich)
• GFN-FF (Geometry, Frequency, and Noncovalent Interaction Force-Field) – a completely automated partially polarizable generic force-field for the accurate description of structures and dynamics of large molecules across the periodic table developed by Stefan Grimme and Sebastian Spicher at the University of Bonn.
• WASABe v1.0 PFF (for Water, orgAnic Solvents, And Battery electrolytes) An isotropic atomic dipole polarizable force field for accurate description of battery electrolytes in terms of thermodynamic and dynamic properties for high lithium salt concentrations in sulfonate solvent by Oleg Starovoytov 
• XED (eXtended Electron Distribution) - a polarizable force-field created as a modification of an atom-centered charge model, developed by Andy Vinter. Partially charged monopoles are placed surrounding atoms to simulate more geometrically accurate electrostatic potentials at a fraction of the expense of using quantum mechanical methods. Primarily used by software packages supplied by Cresset Biomolecular Discovery.

Reactive

• EVB (Empirical valence bond) – reactive force field introduced by Warshel and coworkers for use in modeling chemical reactions in different environments. The EVB facilitates calculating activation free energies in condensed phases and in enzymes.
• ReaxFF – reactive force field (interatomic potential) developed by Adri van Duin, William Goddard and coworkers. It is slower than classical MD (50x), needs parameter sets with specific validation, and has no validation for surface and interfacial energies. Parameters are non-interpretable. It can be used atomistic-scale dynamical simulations of chemical reactions. Parallelized ReaxFF allows reactive simulations on >>1,000,000 atoms on large supercomputers.

Coarse-grained

• DPD (Dissipative particle dynamics) – This is a method commonly applied in chemical engineering. It is typically used for studying the hydrodynamics of various simple and complex fluids which require consideration of time and length scales larger than those accessible to classical Molecular dynamics. The potential was originally proposed by Hoogerbrugge and Koelman  with later modifications by Español and Warren  The current state of the art was well documented in a CECAM workshop in 2008. Recently, work has been undertaken to capture some of the chemical subtitles relevant to solutions. This has led to work considering automated parameterisation of the DPD interaction potentials against experimental observables.
• MARTINI – a coarse-grained potential developed by Marrink and coworkers at the University of Groningen, initially developed for molecular dynamics simulations of lipids,^[6] later extended to various other molecules. The force field applies a mapping of four heavy atoms to one CG interaction site and is parameterized with the aim of reproducing thermodynamic properties.
• SAFT – A top-down coarse-grained model developed in the Molecular Systems Engineering group at Imperial College London fitted to liquid phase densities and vapor pressures of pure compounds by using the SAFT equation of state.
• SIRAH – a coarse-grained force field developed by Pantano and coworkers of the Biomolecular Simulations Group, Institut Pasteur of Montevideo, Uruguay; developed for molecular dynamics of water, DNA, and proteins. Free available for AMBER and GROMACS packages.
• VAMM (Virtual atom molecular mechanics) – a coarse-grained force field developed by Korkut and Hendrickson for molecular mechanics calculations such as large scale conformational transitions based on the virtual interactions of C-alpha atoms. It is a knowledge based force field and formulated to capture features dependent on secondary structure and on residue-specific contact information in proteins.

Machine learning

• MACE (Multi Atomic Cluster Expansion) is a highly accurate machine learning force field architecture that combines the rigorous many-body expansion of the total potential energy with rotationally equivariant representations of the system.
• ANI (Artificial Narrow Intelligence) is a transferable neural network potential, built from atomic environment vectors, and able to provide DFT accuracy in terms of energies.
• FFLUX (originally QCTFF)  A set of trained Kriging models which operate together to provide a molecular force field trained on Atoms in molecules or Quantum chemical topology energy terms including electrostatic, exchange and electron correlation.
• TensorMol, a mixed model, a neural network provides a short-range potential, whilst more traditional potentials add screened long-range terms.
• Δ-ML not a force field method but a model that adds learnt correctional energy terms to approximate and relatively computationally cheap quantum chemical methods in order to provide an accuracy level of a higher order, more computationally expensive quantum chemical model.
• SchNet a Neural network utilising continuous-filter convolutional layers, to predict chemical properties and potential energy surfaces.
• PhysNet is a Neural Network-based energy function to predict energies, forces and (fluctuating) partial charges.

Water

Main article: Water model

The set of parameters used to model water or aqueous solutions (basically a force field for water) is called a water model. Many water models have been proposed; some examples are TIP3P, TIP4P, SPC, flexible simple point charge water model (flexible SPC), ST2, and mW. Other solvents and methods of solvent representation are also applied within computational chemistry and physics; these are termed solvent models.

Modified amino acids

• Forcefield_PTM – An AMBER-based forcefield and webtool for modeling common post-translational modifications of amino acids in proteins developed by Chris Floudas and coworkers. It uses the ff03 charge model and has several side-chain torsion corrections parameterized to match the quantum chemical rotational surface.
• Forcefield_NCAA - An AMBER-based forcefield and webtool for modeling common non-natural amino acids in proteins in condensed-phase simulations using the ff03 charge model. The charges have been reported to be correlated with hydration free energies of corresponding side-chain analogs.

Other

• LFMM (Ligand Field Molecular Mechanics) - functions for the coordination sphere around transition metals based on the angular overlap model (AOM). Implemented in the Molecular Operating Environment (MOE) as DommiMOE and in Tinker
• VALBOND - a function for angle bending that is based on valence bond theory and works for large angular distortions, hypervalent molecules, and transition metal complexes. It can be incorporated into other force fields such as CHARMM and UFF.

Interpretations of quantum mechanics

From Wikipedia, the free encyclopedia
https://en.wikipedia.org/wiki/Interpretations_of_quantum_mechanics

An interpretation of quantum mechanics is an attempt to explain how the mathematical theory of quantum mechanics might correspond to experienced reality. Quantum mechanics has held up to rigorous and extremely precise tests in an extraordinarily broad range of experiments. However, there exist a number of contending schools of thought over their interpretation. These views on interpretation differ on such fundamental questions as whether quantum mechanics is deterministic or stochastic, local or non-local, which elements of quantum mechanics can be considered real, and what the nature of measurement is, among other matters.

While some variation of the Copenhagen interpretation is commonly presented in textbooks, many other interpretations have been developed. Despite nearly a century of debate and experiment, no consensus has been reached among physicists and philosophers of physics concerning which interpretation best "represents" reality.

History

Erwin Schrödinger

 

Max Born

 

Niels Bohr

The definition of quantum theorists' terms, such as wave function and matrix mechanics, progressed through many stages. For instance, Erwin Schrödinger originally viewed the electron's wave function as its charge density smeared across space, but Max Born reinterpreted the absolute square value of the wave function as the electron's probability density distributed across space; the Born rule, as it is now called, matched experiment, whereas Schrödinger's charge density view did not.

The views of several early pioneers of quantum mechanics, such as Niels Bohr and Werner Heisenberg, are often grouped together as the "Copenhagen interpretation", though physicists and historians of physics have argued that this terminology obscures differences between the views so designated. Copenhagen-type ideas were never universally embraced, and challenges to a perceived Copenhagen orthodoxy gained increasing attention in the 1950s with the pilot-wave interpretation of David Bohm and the many-worlds interpretation of Hugh Everett III.

The physicist N. David Mermin once quipped, "New interpretations appear every year. None ever disappear." As a rough guide to development of the mainstream view during the 1990s and 2000s, a "snapshot" of opinions was collected in a poll by Schlosshauer et al. at the "Quantum Physics and the Nature of Reality" conference of July 2011. The authors reference a similarly informal poll carried out by Max Tegmark at the "Fundamental Problems in Quantum Theory" conference in August 1997. The main conclusion of the authors is that "the Copenhagen interpretation still reigns supreme", receiving the most votes in their poll (42%), besides the rise to mainstream notability of the many-worlds interpretations: "The Copenhagen interpretation still reigns supreme here, especially if we lump it together with intellectual offsprings such as information-based interpretations and the quantum Bayesian interpretation. In Tegmark's poll, the Everett interpretation received 17% of the vote, which is similar to the number of votes (18%) in our poll."

Some concepts originating from studies of interpretations have found more practical application in quantum information science.

Nature

More or less, all interpretations of quantum mechanics share two qualities:

1. They interpret a formalism—a set of equations and principles to generate predictions via input of initial conditions
2. They interpret a phenomenology—a set of observations, including those obtained by empirical research and those obtained informally, such as humans' experience of an unequivocal world

Two qualities vary among interpretations:

1. Epistemology—claims about the possibility, scope, and means toward relevant knowledge of the world
2. Ontology—claims about what things, such as categories and entities, exist in the world

In the philosophy of science, the distinction between knowledge and reality is termed epistemic versus ontic. A general law can be seen as a generalisation of the regularity of outcomes (epistemic), whereas a causal mechanism may be thought of as determining or regulating outcomes (ontic). A phenomenon can be interpreted either as ontic or as epistemic. For instance, indeterminism may be attributed to limitations of human observation and perception (epistemic), or may be explained as intrinsic physical randomness (ontic). Confusing the epistemic with the ontic—if for example one were to presume that a general law actually "governs" outcomes, and that the statement of a regularity has the role of a causal mechanism—is a category mistake.

In a broad sense, scientific theory can be viewed as offering an approximately true description or explanation of the natural world (scientific realism) or as providing nothing more than an account of our knowledge of the natural world (antirealism). A realist stance sees the epistemic as giving us a window onto the ontic, whereas an antirealist stance sees the epistemic as providing only a logically consistent picture of the ontic. In the first half of the 20th Century, a key antirealist philosophy was logical positivism, which sought to exclude unobservable aspects of reality from scientific theory.

Since the 1950s antirealism has adopted a more modest approach, often in the form of instrumentalism, permitting talk of unobservables but ultimately discarding the very question of realism and positing scientific theory as a tool to help us make predictions, not to attain a deep metaphysical understanding of the world. The instrumentalist view is typified by David Mermin's famous slogan: "Shut up and calculate" (which is often misattributed to Richard Feynman).

Interpretive challenges

1. Abstract, mathematical nature of quantum field theories: the mathematical structure of quantum mechanics is abstract and does not result in a single, clear interpretation of its quantities.
2. Apparent indeterministic and irreversible processes: in classical field theory, a physical property at a given location in the field is readily derived. In most mathematical formulations of quantum mechanics, measurement (understood as an interaction with a given state) has a special role in the theory, as it is the sole process that can cause a nonunitary, irreversible evolution of the state.
3. Role of the observer in determining outcomes. Copenhagen-type interpretations imply that the wavefunction is a calculational tool, and represents reality only immediately after a measurement performed by an observer. Everettian interpretations grant that all possible outcomes are real, and that measurement-type interactions cause a branching process in which each possibility is realised.
4. Classically unexpected correlations between remote objects: entangled quantum systems, as illustrated in the EPR paradox, obey statistics that seem to violate principles of local causality by action at a distance.
5. Complementarity of proffered descriptions: complementarity holds that no set of classical physical concepts can simultaneously refer to all properties of a quantum system. For instance, wave description A and particulate description B can each describe quantum system S, but not simultaneously. This implies the composition of physical properties of S does not obey the rules of classical propositional logic when using propositional connectives (see "Quantum logic"). Like contextuality, the "origin of complementarity lies in the non-commutativity of operators" that describe quantum objects.
6. Rapidly rising intricacy, far exceeding humans' present calculational capacity, as a system's size increases: since the state space of a quantum system is exponential in the number of subsystems, it is difficult to derive classical approximations.
7. Contextual behaviour of systems locally: Quantum contextuality demonstrates that classical intuitions, in which properties of a system hold definite values independent of the manner of their measurement, fail even for local systems. Also, physical principles such as Leibniz's Principle of the identity of indiscernibles no longer apply in the quantum domain, signaling that most classical intuitions may be incorrect about the quantum world.

Influential interpretations

Copenhagen interpretation

Main article: Copenhagen interpretation

The Copenhagen interpretation is a collection of views about the meaning of quantum mechanics principally attributed to Niels Bohr and Werner Heisenberg. It is one of the oldest attitudes towards quantum mechanics, as features of it date to the development of quantum mechanics during 1925–1927, and it remains one of the most commonly taught. There is no definitive historical statement of what is the Copenhagen interpretation, and there were in particular fundamental disagreements between the views of Bohr and Heisenberg. For example, Heisenberg emphasized a sharp "cut" between the observer (or the instrument) and the system being observed, while Bohr offered an interpretation that is independent of a subjective observer or measurement or collapse, which relies on an "irreversible" or effectively irreversible process that imparts the classical behavior of "observation" or "measurement".

Features common to Copenhagen-type interpretations include the idea that quantum mechanics is intrinsically indeterministic, with probabilities calculated using the Born rule, and the principle of complementarity, which states certain pairs of complementary properties cannot all be observed or measured simultaneously. Moreover, properties only result from the act of "observing" or "measuring"; the theory avoids assuming definite values from unperformed experiments. Copenhagen-type interpretations hold that quantum descriptions are objective, in that they are independent of physicists' mental arbitrariness. The statistical interpretation of wavefunctions due to Max Born differs sharply from Schrödinger's original intent, which was to have a theory with continuous time evolution and in which wavefunctions directly described physical reality.

Many worlds

Main article: Many-worlds interpretation

The many-worlds interpretation is an interpretation of quantum mechanics in which a universal wavefunction obeys the same deterministic, reversible laws at all times; in particular there is no (indeterministic and irreversible) wavefunction collapse associated with measurement. The phenomena associated with measurement are claimed to be explained by decoherence, which occurs when states interact with the environment. More precisely, the parts of the wavefunction describing observers become increasingly entangled with the parts of the wavefunction describing their experiments. Although all possible outcomes of experiments continue to lie in the wavefunction's support, the times at which they become correlated with observers effectively "split" the universe into mutually unobservable alternate histories.

Quantum information theories

Quantum informational approaches have attracted growing support. They subdivide into two kinds.

• Information ontologies, such as J. A. Wheeler's "it from bit". These approaches have been described as a revival of immaterialism.
• Interpretations where quantum mechanics is said to describe an observer's knowledge of the world, rather than the world itself. This approach has some similarity with Bohr's thinking. Collapse (also known as reduction) is often interpreted as an observer acquiring information from a measurement, rather than as an objective event. These approaches have been appraised as similar to instrumentalism. James Hartle writes,

The state is not an objective property of an individual system but is that information, obtained from a knowledge of how a system was prepared, which can be used for making predictions about future measurements. ... A quantum mechanical state being a summary of the observer's information about an individual physical system changes both by dynamical laws, and whenever the observer acquires new information about the system through the process of measurement. The existence of two laws for the evolution of the state vector ... becomes problematical only if it is believed that the state vector is an objective property of the system ... The "reduction of the wavepacket" does take place in the consciousness of the observer, not because of any unique physical process which takes place there, but only because the state is a construct of the observer and not an objective property of the physical system.

Relational quantum mechanics

Main article: Relational quantum mechanics

The essential idea behind relational quantum mechanics, following the precedent of special relativity, is that different observers may give different accounts of the same series of events: for example, to one observer at a given point in time, a system may be in a single, "collapsed" eigenstate, while to another observer at the same time, it may be in a superposition of two or more states. Consequently, if quantum mechanics is to be a complete theory, relational quantum mechanics argues that the notion of "state" describes not the observed system itself, but the relationship, or correlation, between the system and its observer(s). The state vector of conventional quantum mechanics becomes a description of the correlation of some degrees of freedom in the observer, with respect to the observed system. However, it is held by relational quantum mechanics that this applies to all physical objects, whether or not they are conscious or macroscopic. Any "measurement event" is seen simply as an ordinary physical interaction, an establishment of the sort of correlation discussed above. Thus the physical content of the theory has to do not with objects themselves, but the relations between them.

QBism

Main article: Quantum Bayesianism

QBism, which originally stood for "quantum Bayesianism", is an interpretation of quantum mechanics that takes an agent's actions and experiences as the central concerns of the theory. This interpretation is distinguished by its use of a subjective Bayesian account of probabilities to understand the quantum mechanical Born rule as a normative addition to good decision-making. QBism draws from the fields of quantum information and Bayesian probability and aims to eliminate the interpretational conundrums that have beset quantum theory.

QBism deals with common questions in the interpretation of quantum theory about the nature of wavefunction superposition, quantum measurement, and entanglement. According to QBism, many, but not all, aspects of the quantum formalism are subjective in nature. For example, in this interpretation, a quantum state is not an element of reality—instead it represents the degrees of belief an agent has about the possible outcomes of measurements. For this reason, some philosophers of science have deemed QBism a form of anti-realism. The originators of the interpretation disagree with this characterization, proposing instead that the theory more properly aligns with a kind of realism they call "participatory realism", wherein reality consists of more than can be captured by any putative third-person account of it.

Consistent histories

Main article: Consistent histories

The consistent histories interpretation generalizes the conventional Copenhagen interpretation and attempts to provide a natural interpretation of quantum cosmology. The theory is based on a consistency criterion that allows the history of a system to be described so that the probabilities for each history obey the additive rules of classical probability. It is claimed to be consistent with the Schrödinger equation.

According to this interpretation, the purpose of a quantum-mechanical theory is to predict the relative probabilities of various alternative histories (for example, of a particle).

Ensemble interpretation

Main article: Ensemble interpretation

The ensemble interpretation, also called the statistical interpretation, can be viewed as a minimalist interpretation. That is, it claims to make the fewest assumptions associated with the standard mathematics. It takes the statistical interpretation of Born to the fullest extent. The interpretation states that the wave function does not apply to an individual system – for example, a single particle – but is an abstract statistical quantity that only applies to an ensemble (a vast multitude) of similarly prepared systems or particles. In the words of Einstein:

The attempt to conceive the quantum-theoretical description as the complete description of the individual systems leads to unnatural theoretical interpretations, which become immediately unnecessary if one accepts the interpretation that the description refers to ensembles of systems and not to individual systems.

— Einstein in Albert Einstein: Philosopher-Scientist, ed. P.A. Schilpp (Harper & Row, New York)

The most prominent current advocate of the ensemble interpretation is Leslie E. Ballentine, professor at Simon Fraser University, author of the text book Quantum Mechanics, A Modern Development.

De Broglie–Bohm theory

Main article: De Broglie–Bohm theory

The de Broglie–Bohm theory of quantum mechanics (also known as the pilot wave theory) is a theory by Louis de Broglie and extended later by David Bohm to include measurements. Particles, which always have positions, are guided by the wavefunction. The wavefunction evolves according to the Schrödinger wave equation, and the wavefunction never collapses. The theory takes place in a single spacetime, is non-local, and is deterministic. The simultaneous determination of a particle's position and velocity is subject to the usual uncertainty principle constraint. The theory is considered to be a hidden-variable theory, and by embracing non-locality it satisfies Bell's inequality. The measurement problem is resolved, since the particles have definite positions at all times. Collapse is explained as phenomenological.

Transactional interpretation

Main article: Transactional interpretation

The transactional interpretation of quantum mechanics (TIQM) by John G. Cramer is an interpretation of quantum mechanics inspired by the Wheeler–Feynman absorber theory.^[42] It describes the collapse of the wave function as resulting from a time-symmetric transaction between a possibility wave from the source to the receiver (the wave function) and a possibility wave from the receiver to source (the complex conjugate of the wave function). This interpretation of quantum mechanics is unique in that it not only views the wave function as a real entity, but the complex conjugate of the wave function, which appears in the Born rule for calculating the expected value for an observable, as also real.

Von Neumann–Wigner interpretation

Main article: Von Neumann–Wigner interpretation

In his treatise The Mathematical Foundations of Quantum Mechanics, John von Neumann deeply analyzed the so-called measurement problem. He concluded that the entire physical universe could be made subject to the Schrödinger equation (the universal wave function). He also described how measurement could cause a collapse of the wave function. This point of view was prominently expanded on by Eugene Wigner, who argued that human experimenter consciousness (or maybe even dog consciousness) was critical for the collapse, but he later abandoned this interpretation.

However, consciousness remains a mystery. The origin and place in nature of consciousness are not well understood. Some specific proposals for consciousness caused wave-function collapse have been shown to be unfalsifiable.

Quantum logic

Main article: Quantum logic

Quantum logic can be regarded as a kind of propositional logic suitable for understanding the apparent anomalies regarding quantum measurement, most notably those concerning composition of measurement operations of complementary variables. This research area and its name originated in the 1936 paper by Garrett Birkhoff and John von Neumann, who attempted to reconcile some of the apparent inconsistencies of classical Boolean logic with the facts related to measurement and observation in quantum mechanics.

Modal interpretations of quantum theory

Modal interpretations of quantum mechanics were first conceived of in 1972 by Bas van Fraassen, in his paper "A formal approach to the philosophy of science". Van Fraassen introduced a distinction between a dynamical state, which describes what might be true about a system and which always evolves according to the Schrödinger equation, and a value state, which indicates what is actually true about a system at a given time. The term "modal interpretation" now is used to describe a larger set of models that grew out of this approach. The Stanford Encyclopedia of Philosophy describes several versions, including proposals by Kochen, Dieks, Clifton, Dickson, and Bub. According to Michel Bitbol, Schrödinger's views on how to interpret quantum mechanics progressed through as many as four stages, ending with a non-collapse view that in respects resembles the interpretations of Everett and van Fraassen. Because Schrödinger subscribed to a kind of post-Machian neutral monism, in which "matter" and "mind" are only different aspects or arrangements of the same common elements, treating the wavefunction as ontic and treating it as epistemic became interchangeable.

Time-symmetric theories

Time-symmetric interpretations of quantum mechanics were first suggested by Walter Schottky in 1921. Several theories have been proposed that modify the equations of quantum mechanics to be symmetric with respect to time reversal. (See Wheeler–Feynman time-symmetric theory.) This creates retrocausality: events in the future can affect ones in the past, exactly as events in the past can affect ones in the future. In these theories, a single measurement cannot fully determine the state of a system (making them a type of hidden-variables theory), but given two measurements performed at different times, it is possible to calculate the exact state of the system at all intermediate times. The collapse of the wavefunction is therefore not a physical change to the system, just a change in our knowledge of it due to the second measurement. Similarly, they explain entanglement as not being a true physical state but just an illusion created by ignoring retrocausality. The point where two particles appear to "become entangled" is simply a point where each particle is being influenced by events that occur to the other particle in the future.

Not all advocates of time-symmetric causality favour modifying the unitary dynamics of standard quantum mechanics. Thus a leading exponent of the two-state vector formalism, Lev Vaidman, states that the two-state vector formalism dovetails well with Hugh Everett's many-worlds interpretation.

Other interpretations

Main article: Minority interpretations of quantum mechanics

As well as the mainstream interpretations discussed above, a number of other interpretations have been proposed that have not made a significant scientific impact for whatever reason. These range from proposals by mainstream physicists to the more occult ideas of quantum mysticism.

Related concepts

Some ideas are discussed in the context of interpreting quantum mechanics but are not necessarily regarded as interpretations themselves.

Quantum Darwinism

Main article: Quantum Darwinism

Quantum Darwinism is a theory meant to explain the emergence of the classical world from the quantum world as due to a process of Darwinian natural selection induced by the environment interacting with the quantum system; where the many possible quantum states are selected against in favor of a stable pointer state. It was proposed in 2003 by Wojciech Zurek and a group of collaborators including Ollivier, Poulin, Paz and Blume-Kohout. The development of the theory is due to the integration of a number of Zurek's research topics pursued over the course of twenty-five years including pointer states, einselection and decoherence.

Objective-collapse theories

Main article: Objective-collapse theory

Objective-collapse theories differ from the Copenhagen interpretation by regarding both the wave function and the process of collapse as ontologically objective (meaning these exist and occur independent of the observer). In objective theories, collapse occurs either randomly ("spontaneous localization") or when some physical threshold is reached, with observers having no special role. Thus, objective-collapse theories are realistic, indeterministic, no-hidden-variables theories. Standard quantum mechanics does not specify any mechanism of collapse; quantum mechanics would need to be extended if objective collapse is correct. The requirement for an extension means that objective-collapse theories are alternatives to quantum mechanics rather than interpretations of it. Examples include

• the Ghirardi–Rimini–Weber theory
• the continuous spontaneous localization model
• the Penrose interpretation

Comparisons

The most common interpretations are summarized in the table below. The values shown in the cells of the table are not without controversy, for the precise meanings of some of the concepts involved are unclear and, in fact, are themselves at the center of the controversy surrounding the given interpretation. For another table comparing interpretations of quantum theory, see reference.

No experimental evidence exists that distinguishes among these interpretations. To that extent, the physical theory stands, and is consistent with itself and with reality. Nevertheless, designing experiments that would test the various interpretations is the subject of active research.

Most of these interpretations have variants. For example, it is difficult to get a precise definition of the Copenhagen interpretation as it was developed and argued by many people.