Quantum mechanics casts its shadows before it It might be felt amazing that quantum effects show up in our macroscopic world. We know miraculous phenomena such as superconductivity, for instance, which classical physics is basically unable to explain. This makes it impossible to separate nicely the microcosm from the macroscopic world through a clear-cut borderline, or a more or less well defined transition region at least. It should be noticed that classical physics, notably statistical thermodynamics, in certain cases already runs into trouble in what should be its domain of validity. This became obvious from observations, mostly at low temperatures, that manifestly differed from basic classical predictions. Those discrepancies were found, above all, in thermodynamics. In particular, the specific heat capacity of materials with decreasing temperature did not obey the rule that followed from classical (i.e., Boltzmann) statistics. This rule states that the energy can be calculated by assigning to any constituent the average energy kT /2 ( k Boltzmann constant) per degree of motional freedom. (In the case of vibrations the potential energy gives rise to an extra contribution kT /2.) For instance, in an ideal gas formed from atoms, any atom has three translational degrees of freedom. Hence each atom contributes the energy 3 kT /2, and we simply get the total energy of the sample on multiplication of this figure by the number of atoms. When the constituents of a gas are molecules, additional rotational and vibrational degrees of freedom come into play, which further enhance the average energy of a molecule.
Quantum mechanics casts its shadows before it It might be felt amazing that quantum effects show up in our macroscopic world. We know miraculous phenomena such as superconductivity, for instance, which classical physics is basically unable to explain. This makes it impossible to separate nicely the microcosm from the macroscopic world through a clear-cut borderline, or a more or less well defined transition region at least. It should be noticed that classical physics, notably statistical thermodynamics, in certain cases already runs into trouble in what should be its domain of validity. This became obvious from observations, mostly at low temperatures, that manifestly differed from basic classical predictions. Those discrepancies were found, above all, in thermodynamics. In particular, the specific heat capacity of materials with decreasing temperature did not obey the rule that followed from classical (i.e., Boltzmann) statistics. This rule states that the energy can be calculated by assigning to any constituent the average energy kT /2 ( k Boltzmann constant) per degree of motional freedom. (In the case of vibrations the potential energy gives rise to an extra contribution kT /2.) For instance, in an ideal gas formed from atoms, any atom has three translational degrees of freedom. Hence each atom contributes the energy 3 kT /2, and we simply get the total energy of the sample on multiplication of this figure by the number of atoms. When the constituents of a gas are molecules, additional rotational and vibrational degrees of freedom come into play, which further enhance the average energy of a molecule.
Envisioned by Richard Feynman in the early 1980s, quantum simulation has received dramatic impetus thanks to the development of a variety of plateforms able to emulate a wide class of quantum Hamiltonians.During the past decade, most of the quantum simulators have implemented rather well-known models, hence permitting a direct comparison with theoretical calculations and a precise benchmarking of their reliability.The field has now reached a maturity such that one can address difficult problems, which cannot be solved efficiently using classical algorithms.These advances provide unprecedented opportunities to explore previously unreachable fields, test theoretical predictions, and inspire novel approaches.This contribution is an elementary introduction to quantum simulation.We discuss the challenges, define both digital and analog quantum simulators, and list the demanding conditions they require.We also provide a brief account of the contributions gathered in the dossier on Quantum simulation in the Compte rendus Physique of the French Academy of Sciences [1][2][3][4][5][6].The latter completes excellent reviews that appeared previously, see for instance . Universal models and the role of simulations in many-body physicsUnderstanding the behavior of macroscopic quantum systems is a major challenge of modern physics.The basic laws of low-energy physics are by now quite well known at the microscopic, say atomic, scale.Conversely, many fundamental questions remain open, and even debated, about the collective dynamics at the macroscopic scale.By "macroscopic scale", here we mean systems made up of a huge number of constituents, or degrees of freedom, say 10 6 , 10 23 , or even more, as relevant in condensed matter physics or in astrophysics, for instance.Such huge systems cannot be treated exactly, be it a the classical level and, even worse, at the quantum level.Yet, it is the main outcome of the thermodynamic approach that the collective behavior of a macroscopic system can drastically differ from that of its elementary constituents.For instance, the elementary interactions between the H 2 O molecules are fundamentally unchanged when a water bucket turns from the liquid phase to the solid phase at zero degree Celsius.Similarly, the interactions between the microscopic magnetic moments do not show any brutal change when a magnetic material gets magnetized underneath the Curie temperature.Hence, the dramatic effects observed in macroscopic systems are governed by large-scale instabilities, without obvious counterparts at the microscopic level.This observation takes a universal character, summarized in the celebrated motto "More is Different" [15].Such so-called emerging phenomena also appear in quantum systems, where new effects that are impossible in the classical world show up below some critical temperature or at zero temperature when some interaction parameter passes through a critical value.Celebrated examples include the superfluid transition in helium or super-conducting transitions and other metal-insulator transitions in electronic systems.Strikingly enough at first sight, while emerging phenomena only appear in very large scale macroscopic systems, their germs are contained in the mutual interactions of their elementary constituents.Hence, local two-body interactions are sufficient to explain a huge class of phase transitions, such as the liquid-solid and magnetic transitions mentioned above.The Boltzmann statistical approach proved particularly successful in describing this connection between the microscopic and macroscopic scales.To understand emerging phenomena on grounds as fundamental as possible, the programme is now well established: One tries to identify the basic microscopic terms that seem to be relevant and disregards all the other microscopic details.One then elaborates a model, as generic as possible, likely to reproduce the main experimental observations.The most usual examples are the Ising and Heisenberg models for magnetic transitions, or the Hubbard model for metal-insulator transitions [16][17][18].Then all is left to do is to check that the phenomenon of interest indeed emerges from the dynamics of the simplified model.The realization of this programme is nothing but a simulation.It consists in building up a simplified system that mimics the main properties of a real system.
525. IN preceding chapters we saw how the classical system of mechanics failed to account for certain phenomena of physics, and it became clear that these could only be explained in terms of a new system of dynamics which must be supposed to supersede the old classical system when we have to deal with phenomena conditioned by the fine-scale structure of matter. The first instance of the failure of the classical mechanics was provided by the phenomenon of black-body radiation. On the assumption that black-body radiation represents a state of thermodynamical equilibrium, we found that the observed distribution of radiant energy in the spectrum of an ideal black body could be explained on the supposition that the energy of each part of the radiation-producing mechanism fell into “quanta.” Corresponding to a simple harmonic vibration of frequency v , there was supposed to be an energyquantum of amount hv , where h is Planck's universal constant of which the value has already been given. Calling this energy ∈ , it was found that the energy of vibration could be 0, ∈, 2∈, 3∈,… or any integral multiple of ∈ , but could not contain fractional parts of ∈ . The energy, after retaining one of these values for a certain time, had to be supposed to jump abruptly to some other value, which in turn was retained until another jump occurred.
Since its very beginning, quantum mechanics has been developed to deal with systems on the atomic or sub-atomic scale. For many decades, there has been no reason to think about its application to macroscopic systems. Actually, macroscopic objects have even been used to show how bizarre quantum effects would appear if quantum mechanics were applied beyond its original realm. This is, for example, the essence of the so-called Schrödinger cat paradox (Schrödinger, 1935). How-ever, due to recent advances in the design of systems on the meso- and nanoscopic scales, as well as in cryogenic techniques, this situation has changed drastically. It is now quite natural to ask whether a specific quantum effect, collectively involving a macroscopic number of particles, could occur in these systems. In this book it is our intention to address the quantum mechanical effects that take place in properly chosen or built “macroscopic” systems. Starting from a very naïve point of view, we could always ask what happens to systems whose classical dynamics can be described by equations of motion equivalent to those of particles (or fields) in a given potential (or potential energy density). These can be represented by a generalized “coordinate” φ( r , t ) which could either describe a field variable or a “point particle” if it is not position dependent, φ( r , t ) = φ( t ).
It is widely believed that the microscopic, that is, atomic-scale or smaller, world is governed by quantum mechanics while the macroscopic world, where our direct and daily experiences reside, is governed by classical mechanics. But why? Why do we not observe quantum phenomena such as quantum tunneling and quantum superposition in the macroscopic world? Where is the boundary between the microscopic and macroscopic worlds when it comes to the governing physical principles? Macroscopic quantum phenomena were first examined theoretically by A. Leggett in the 1970s. This boldly audacious idea was experimentally demonstrated in a series of groundbreaking works on Josephson junctions by John Clarke, Michel Devoret, and John Martinis in 1985, that have been celebrated by the 2025 Nobel Prize in Physics. The trio’s work spurred the development of various qubit types based on superconducting circuits, ultimately leading to the current advancement of superconducting quantum computers.
The basic concepts of statistical mechanics and its application to many-body systems, phase transitions and critical phenomena will be discussed briefly in this chapter. We will be using these ideas frequently in the subsequent lectures. Statistical mechanics describes the thermodynamic behaviour of macroscopic systems from the laws which govern the behaviour of the constituent elements at the microscopic level. The microscopic elements can be atoms, molecules, dipole moments or magnetic moments, etc. A macroscopic system is generally composed of a large number of these elements (of the order of Avogadro number N A ≈ 6.022 × 1023 per mole). Each element may have a large number of internal degrees of freedom associated with different types of motion such as translation, rotation, vibration etc. The constituent elements may interact with the external field applied to the system. There can also be very complex interaction among the constituent elements. The macroscopic properties of a system in the thermodynamic limit is thus determined by the properties of the constituent molecules, their interaction with external field as well as interaction among themselves. For a system of N elements, volume V and density ρ, the thermodynamic limit is defined as lim N → ∞, lim V → ∞ keeping ρ = N/V finite. In this limit, the extensive properties of the system become directly proportional to the size of the system (N or V), while the intensive properties become independent of the size of the system.
In this study, we present a quantum-statistical analysis of H2 and LiH diatomic molecules within the Frost--Musulin potential framework. By combining the analytical bound-state approach to the radial Schrödinger problem with the near-equilibrium Pekeris representation, we obtain a validated rotation-vibration spectrum that reproduces a physically consistent ordering of energy levels. These bound states are subsequently combined with standard translational and rotational ideal gas contributions to construct the total partition function and the corresponding thermodynamic observables of the ground state. The resulting formulation captures the Gibbs free energy deviation function for both molecules with high quantitative accuracy and provides chemically plausible trends for heat capacity and enthalpy increase over a wide temperature range. At the same time, residual errors become increasingly pronounced in derivative-sensitive quantities, particularly at high temperatures; this indicates that the dominant limitations now stem not from the local bound-state spectrum itself, but from the neglect of inelastic rotational, continuity contributions and dynamics close to dissociation. Consequently, the present results define the potential model as a compact and analytically tractable representation of the bound region, recovering a significant portion of the observed thermochemistry whilst also delineating the regime where more comprehensive molecular statistical mechanics is required.