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CRC Press eBooks

Atoms and Molecules

Phuong Mai Dinh, Jesús Navarro, E. Suraud

Published Dec 2, 2024• 0 citations
Publisher

Abstract

To dedicate a chapter to atoms and molecules in a book on quantum fluids may seem surprising at first glance. Indeed, atoms and molecules are both composite systems, possibly massive, and the first intuition is to follow the analysis of Chapter 1 , where we have classically hierarchized phases of matter according to pressure, temperature and volume. However, when looking in more detail at a standard phase diagram (see for example the case of CO 2 or water in Figure 1.3 ), one soon realizes that it exhibits many other possible interesting paths. In particular, the low pressure/low temperature limit provides an interesting region to explore and actually provides a different scenario. Indeed, in this limit, the single possible phase transition is between gas and solid. But mind that it corresponds to a very low pressure/temperature domain. There are in particular no thermal effects possibly blurring the behavior of the system. We have already seen that boson and fermion gases in their degenerate limits at zero temperature exhibit remarkable features. this particular domain of vanishing temperatures. Both atoms and molecules, depending on their total spin, can be either fermions or bosons.

DOI
10.1201/9781003576587-8

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We have seen in Chapter 3 , that as temperature is increased quantum statistics, both Bose-Einstein or Fermi-Dirac, tend to classical. High temperatures blur out quantum effects in a system, which can be safely described in classical terms. In this chapter, we will consider some systems which manifest quantum properties at macroscopic level, but at very low temperatures. We recall that helium is the only substance which remains liquid at low temperature, down to absolute zero (see Chapter 6 ), a phenomenon related to the quantum behavior of its constituent atoms. Liquid helium was instrumental to the discovery that some metals are able to sustain an electrical current for long periods of time without any driving force. This phenomenon is named superconductivity, and is also a macroscopic manifestation of the quantum behavior of the electrons in metals. Later on it was discovered that liquid helium itself shows a similar property, named superfluidity, consisting in its ability to flow through a capillary without viscosity. Hence, a persistent flow of liquid can be maintained without any driving force. While the quantum agents of superconductivity are electrons, which are spin- 1/2 fermions, those of superfluidity are 4 He atoms, which are spin- 0 bosons. There are other systems able to display similar behavior as liquid 3 He, atomic nuclei and nuclear matter. In fact, superfluidity and superconductivity are new phases of matter related to the bosonic character of 4 He atoms or of pairs of fermions (either electrons, 3 He atoms or nucleons), the same as Bose-Einstein condensation in ultracold atomic gases. The temperatures where these new phases manifest range from 165 K for superconductivity down to a few nano-Kelvin for Bose-Einstein condensation.

CRC Press eBooks•Dec 2, 2024•0 citations

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Introduction In most of the discussion presented so far in this book, the quantum character of atoms and electrons has been ignored. The Ising spin models have been an exception, but since the Ising Hamiltonian is diagonal (in the absence of a transverse magnetic field), all energy eigenvalues are known and the Monte Carlo sampling can be carried out just as in the case of classical statistical mechanics. Furthermore, the physical properties are in accord with the third law of thermodynamics for Ising-type Hamiltonians (e.g. entropy S and specific heat vanish for temperature T → 0, etc.) in contrast to the other truly classical models dealt with in previous chapters (e.g. classical Heisenberg spin models, classical fluids and solids, etc.) which have many unphysical low temperature properties. A case in point is a classical solid for which the specific heat follows the Dulong–Petit law, C = 3 Nk B , as T → 0, and the entropy has unphysical behavior since S → –∞. Also, thermal expansion coefficients tend to non-vanishing constants for T → 0 while the third law implies that they must be zero. While the position and momentum of a particle can be specified precisely in classical mechanics, and hence the groundstate of a solid is a perfectly rigid crystal lattice (motionless particles localized at the lattice points), in reality the Heisenberg uncertainty principle forbids such a perfect rigid crystal, even at T → 0, due to zero point motions which ‘smear out’ the particles over some region around these lattice points. This delocalization of quantum-mechanical particles increases as the atomic mass is reduced; therefore, these quantum effects are most pronounced for light atoms like hydrogen in metals, or liquid helium. Spectacular phenomena like superfluidity are a consequence of the quantum nature of the particles and have no classical counterpart at all. Even for heavier atoms, which do not show superfluidity because the fluid–solid transition intervenes before a transition from normal fluid to superfluid could occur, there are genuine effects of quantum nature. Examples include the isotope effects (remember that in classical statistical mechanics the kinetic energy part of the Boltzmann factor cancels out from all averages, and thus in thermal equilibrium no property depends explicitly on the mass of the particles).

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Just a couple decades ago bosonic low-temperature physics was synonymous with one particular liquid at a temperature of several degrees Kelvin. This liquid, helium-4, and its famous Helium-II phase, has revealed remarkable quantum properties such as quantized vortices and second sound. Yet, despite many things learned by investigating helium, its study has certain limitations. On the one hand, helium is a strongly interacting liquid, which makes first-principles theoretical research challenging. To name one example, establishing a connection between the non-interacting condensate state described by Bose and Einstein, and the helium properties observed in the lab took decades. Furthermore, helium is a specific chemical element, and hence there is no surprise that its physical properties are fixed by nature. However, every particular chemical element has particular physical properties, so for a long time it seemed that it was as good as it gets. The picture has changed drastically when the first Bose-Einstein condensate (BEC) was observed in an ultracold atomic gas. “Low temperature” has become synonymous with “ultracold”, and the latter implies temperatures on the order of nanokelvins. Most strikingly, the relationship between what is fixed by nature and what is experimentally changeable has evolved. In particular, systems of different particle statistics, spin, and interactions have been engineered using ultracold vapours of various alkali atoms. This versatile manipulation not only makes emulating various condensed-matter physics models in a controlled system without impurities possible, but also opens a path towards novel phenomena that are at present not achievable in any other manner. In this thesis, we have explored some of the novel phenomena that arise in systems of bosonic particles with internal degrees of freedom, such as (pseudo)spin and electric dipole moment. In the introduction, we describe a ferromagnetically coupled spin-1/2 Bose gas with contact interactions in the mean- field approximation. In particular, we compute and discuss the phase diagram of this gas, since it is a simple system which nevertheless has two order parameters. In the chapters that follow, the ideas touched upon in the introduction are developed in more detail. In Chapter 2 we develop a hydrodynamic description of the ferromagnetic spin-1/2 Bose gas at arbitrary temperatures. We study magnetization relaxation and geometric forces. In particular, we consider the topological Hall effect due to the presence of a skyrmion. In Chapter 3 we investigate the miscible (non-ferromagnetic) spin-1/2 Bose gas at arbitrary temperatures, construct its hydrodynamic description, calculate the thermodynamic properties, and study the collective modes of this system. In Chapter 4 we discuss the influence of the off-diagonal Berry curvature on the Bose-Einstein condensation temperature. Finally, in Chapter 5 we study a Bose-Einstein condensate of dipolar molecules in a weak electric field and find it to be described by a quantum rotor model. Moreover, we show that the molecular Bose-Einstein condensate is a ferroelectric material that is fully disordered by quantum fluctuations.

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From a certain temperature on, the molecules “condense” without attractive forces; that is, they accumulate at zero velocity. The theory is pretty, but is there also some truth to it? Albert Einstein, Letter to Ehrenfest (Dec. 1924). Abraham Pais, Subtle Is the Lord: The Science and the Life of Albert Einstein , Oxford University Press, New York (1982) Introduction For over 50 years the low-temperature liquid state of uncharged, spinless He 4 was the only system in which a Bose–Einstein (BE) condensation was considered experimentally realized. In that case, cold (<2.19K) liquid He 4 passes into an extraordinary phase of matter called a superfluid , in which the liquid's viscosity and entropy become zero. With advances in atomic cooling (to ≈ 10 –9 K) the number of Bose systems which demonstrably pass into a condensate has considerably increased. These include several isotopes of alkali gas atoms as well as fermionic atoms that pair into integerspin (boson) composites. Although an ideal Bose gas does exhibit a low-temperature critical instability, the ideal BE gas theory is not, on its own, able to describe the BE condensate wave state. In order for a theory of bosons to account for a condensate wave state, interactions between the bosons must be included. Nevertheless, considerable interesting physics is contained in the ideal Bose gas model.

Cambridge University Press eBooks•Oct 27, 2011•0 citations
To dedicate a chapter to atoms and molecules in a book on quantum fluids may seem surprising at first glance. Indeed, atoms and molecules are both composite systems, possibly massive, and the first intuition is to follow the analysis of Chapter 1 , where we have classically hierarchized phases of matter according to pressure, temperature and volume. However, when looking in more detail at a standard phase diagram (see for example the case of CO 2 or water in Figure 1.3 ), one soon realizes that it exhibits many other possible interesting paths. In particular, the low pressure/low temperature limit provides an interesting region to explore and actually provides a different scenario. Indeed, in this limit, the single possible phase transition is between gas and solid. But mind that it corresponds to a very low pressure/temperature domain. There are in particular no thermal effects possibly blurring the behavior of the system. We have already seen that boson and fermion gases in their degenerate limits at zero temperature exhibit remarkable features. this particular domain of vanishing temperatures. Both atoms and molecules, depending on their total spin, can be either fermions or bosons.
We have seen in Chapter 3 , that as temperature is increased quantum statistics, both Bose-Einstein or Fermi-Dirac, tend to classical. High temperatures blur out quantum effects in a system, which can be safely described in classical terms. In this chapter, we will consider some systems which manifest quantum properties at macroscopic level, but at very low temperatures. We recall that helium is the only substance which remains liquid at low temperature, down to absolute zero (see Chapter 6 ), a phenomenon related to the quantum behavior of its constituent atoms. Liquid helium was instrumental to the discovery that some metals are able to sustain an electrical current for long periods of time without any driving force. This phenomenon is named superconductivity, and is also a macroscopic manifestation of the quantum behavior of the electrons in metals. Later on it was discovered that liquid helium itself shows a similar property, named superfluidity, consisting in its ability to flow through a capillary without viscosity. Hence, a persistent flow of liquid can be maintained without any driving force. While the quantum agents of superconductivity are electrons, which are spin- 1/2 fermions, those of superfluidity are 4 He atoms, which are spin- 0 bosons. There are other systems able to display similar behavior as liquid 3 He, atomic nuclei and nuclear matter. In fact, superfluidity and superconductivity are new phases of matter related to the bosonic character of 4 He atoms or of pairs of fermions (either electrons, 3 He atoms or nucleons), the same as Bose-Einstein condensation in ultracold atomic gases. The temperatures where these new phases manifest range from 165 K for superconductivity down to a few nano-Kelvin for Bose-Einstein condensation.
Introduction In this chapter we provide a comprehensive and unified treatment of the physical concepts and quantities relevant to phase transitions and critical phenomena. Some of these concepts and quantities have already been discussed in the particular contexts of magnetism (Chapter 7), or liquid crystals (Chapter 9, We conclude the chapter with a brief reference to the application of renormalisation group ideas to critical phenomena. The resulting reconciliation of the predictions of classical theories with experiments and exact or quasi-exact solutions of model systems is a major triumph of twentieth-century physics. Phases and phase transitions Thermodynamics habitually deals with equilibrium systems that are uniform on the macroscopic scale – i.e., where the structure, density and composition are the same throughout the bulk of the system, which is many times greater than a single atom or molecule. Because the system is in equilibrium, intensive thermodynamic variables such as the temperature or chemical potential are also spatially uniform. Such a system is said to consist of a single phase – it is a one-phase system. Phases are what used to be called the states of matter. Solids, liquids, gases and plasmas are four commonly occurring phases – they correspond to the four elements of Aristotelian physics: earth, water, air and fire, respectively. There are, however, many other, less easily identified phases, some of which we have already encountered in this book, such as the ferromagnetic, antiferromagnetic, nematic or superconducting phases. On varying the temperature, pressure and chemical potential(s) of a system, properties such as its structure, density, composition, compressibility, specific heat, etc., in general change smoothly. Yet under certain conditions the changes may be abrupt – some of these properties may exhibit discontinuities, or even divergences, at a phase transition . Phase transitions are among the most spectacular phenomena of nature. Consider, for instance, the phase sequence of water on heating: from ice, an opaque, slippery, rock-like solid; to colourless, incompressible, liquid water, which nevertheless easily flows under gravity; to water vapour, an invisible and very low-density (greenhouse!) gas, hence of ill-defined volume.
Introduction In most of the discussion presented so far in this book, the quantum character of atoms and electrons has been ignored. The Ising spin models have been an exception, but since the Ising Hamiltonian is diagonal (in the absence of a transverse magnetic field), all energy eigenvalues are known and the Monte Carlo sampling can be carried out just as in the case of classical statistical mechanics. Furthermore, the physical properties are in accord with the third law of thermodynamics for Ising-type Hamiltonians (e.g. entropy S and specific heat vanish for temperature T → 0, etc.) in contrast to the other truly classical models dealt with in previous chapters (e.g. classical Heisenberg spin models, classical fluids and solids, etc.) which have many unphysical low temperature properties. A case in point is a classical solid for which the specific heat follows the Dulong–Petit law, C = 3 Nk B , as T → 0, and the entropy has unphysical behavior since S → –∞. Also, thermal expansion coefficients tend to non-vanishing constants for T → 0 while the third law implies that they must be zero. While the position and momentum of a particle can be specified precisely in classical mechanics, and hence the groundstate of a solid is a perfectly rigid crystal lattice (motionless particles localized at the lattice points), in reality the Heisenberg uncertainty principle forbids such a perfect rigid crystal, even at T → 0, due to zero point motions which ‘smear out’ the particles over some region around these lattice points. This delocalization of quantum-mechanical particles increases as the atomic mass is reduced; therefore, these quantum effects are most pronounced for light atoms like hydrogen in metals, or liquid helium. Spectacular phenomena like superfluidity are a consequence of the quantum nature of the particles and have no classical counterpart at all. Even for heavier atoms, which do not show superfluidity because the fluid–solid transition intervenes before a transition from normal fluid to superfluid could occur, there are genuine effects of quantum nature. Examples include the isotope effects (remember that in classical statistical mechanics the kinetic energy part of the Boltzmann factor cancels out from all averages, and thus in thermal equilibrium no property depends explicitly on the mass of the particles).
Just a couple decades ago bosonic low-temperature physics was synonymous with one particular liquid at a temperature of several degrees Kelvin. This liquid, helium-4, and its famous Helium-II phase, has revealed remarkable quantum properties such as quantized vortices and second sound. Yet, despite many things learned by investigating helium, its study has certain limitations. On the one hand, helium is a strongly interacting liquid, which makes first-principles theoretical research challenging. To name one example, establishing a connection between the non-interacting condensate state described by Bose and Einstein, and the helium properties observed in the lab took decades. Furthermore, helium is a specific chemical element, and hence there is no surprise that its physical properties are fixed by nature. However, every particular chemical element has particular physical properties, so for a long time it seemed that it was as good as it gets. The picture has changed drastically when the first Bose-Einstein condensate (BEC) was observed in an ultracold atomic gas. “Low temperature” has become synonymous with “ultracold”, and the latter implies temperatures on the order of nanokelvins. Most strikingly, the relationship between what is fixed by nature and what is experimentally changeable has evolved. In particular, systems of different particle statistics, spin, and interactions have been engineered using ultracold vapours of various alkali atoms. This versatile manipulation not only makes emulating various condensed-matter physics models in a controlled system without impurities possible, but also opens a path towards novel phenomena that are at present not achievable in any other manner. In this thesis, we have explored some of the novel phenomena that arise in systems of bosonic particles with internal degrees of freedom, such as (pseudo)spin and electric dipole moment. In the introduction, we describe a ferromagnetically coupled spin-1/2 Bose gas with contact interactions in the mean- field approximation. In particular, we compute and discuss the phase diagram of this gas, since it is a simple system which nevertheless has two order parameters. In the chapters that follow, the ideas touched upon in the introduction are developed in more detail. In Chapter 2 we develop a hydrodynamic description of the ferromagnetic spin-1/2 Bose gas at arbitrary temperatures. We study magnetization relaxation and geometric forces. In particular, we consider the topological Hall effect due to the presence of a skyrmion. In Chapter 3 we investigate the miscible (non-ferromagnetic) spin-1/2 Bose gas at arbitrary temperatures, construct its hydrodynamic description, calculate the thermodynamic properties, and study the collective modes of this system. In Chapter 4 we discuss the influence of the off-diagonal Berry curvature on the Bose-Einstein condensation temperature. Finally, in Chapter 5 we study a Bose-Einstein condensate of dipolar molecules in a weak electric field and find it to be described by a quantum rotor model. Moreover, we show that the molecular Bose-Einstein condensate is a ferroelectric material that is fully disordered by quantum fluctuations.
Pairing and topological phases in cold atoms with long range interactions Chapter 1 Introduction The systematic study and classification of phase transitions has become a popular research area in physics over the past decades. The most familiar phenomena associated to the concept of phase transition are the ones giving rise to macroscopic changes in the properties of strongly correlated many-body systems due to thermal fluctuations. The most prominent examples of this kind of behaviour are the ferromagnetic-paramagnetic transition in lattice spin models and the liquid-gas transition. On the other hand, when dealing with quantum-mechanical systems changes of matter from one state to another can arise as the result of the variation of parameters other than temperature. In particular, when a given many-body quantum problem is studied at zero temperature, thereby suppressing thermal fluctuations, it is the interplay between kinetic energy and interactions that can cause the system to jump into different phases as the model parameters are varied. Phase transitions occurring at zero temperature are widely known as quantum phase transitions. In the framework of the physics of phase transitions, the role of dimensionality is a noticeable one. The major challenge in this perspective is the treatment of low dimensional systems, where standard mean-field treatments and ordinary perturbation theory are known to fail due to the enhancement of fluctuations. The goal of describing collective behaviours in reduced dimensionality is usually pursued in one-dimensional (1D) systems, which turn out to be simple enough to be studied in an effective way through both numerical and analytical techniques, while exhibiting a rich and deeply fascinating phenomenology. As a matter of fact, since particles confined to one dimension cannot avoid interactions with each other, the typical low energy excitations of the system are represented by collective density waves, which substitute nearly free quasiparticle excitations characterizing the behaviour of three-dimensional Fermi liquids in the description of the effects of the interplay between kinetic fluctuations and interactions. On the other hand, the tools employed in the activity of tackling 1D manybody problems are efficient and well developed. The analytical techniques aremainly based on the bosonization technique, which allows for the reformulation of strongly correlated 1D systems onto free bosonic theories, which can then be analyzed by means of standard path integral techniques. Meanwhile, the density matrix renormalization group (DMRG) algorithm represents the state-of-theart numerical machinery in the study of 1D physics, since it allows to efficiently extract the low energy properties of the model Hamiltonian and consequently characterize the corresponding phase diagram by means of the behaviour of properly chosen order parameters. As a final remark pointing out the relevance of the research effort in the direction of a better understanding of 1D many-body quantum systems, it is worth noticing that 1D systems do not represent only a playground for theorists, but have been experimentally realized by means of setups with cold atoms trapped in optical lattices, where the experimentalist is able to tune the model parameters by varying the characteristic features of the trapping laser beams and meanwhile has a comfortable access to the most relevant observables.
From a certain temperature on, the molecules “condense” without attractive forces; that is, they accumulate at zero velocity. The theory is pretty, but is there also some truth to it? Albert Einstein, Letter to Ehrenfest (Dec. 1924). Abraham Pais, Subtle Is the Lord: The Science and the Life of Albert Einstein , Oxford University Press, New York (1982) Introduction For over 50 years the low-temperature liquid state of uncharged, spinless He 4 was the only system in which a Bose–Einstein (BE) condensation was considered experimentally realized. In that case, cold (<2.19K) liquid He 4 passes into an extraordinary phase of matter called a superfluid , in which the liquid's viscosity and entropy become zero. With advances in atomic cooling (to ≈ 10 –9 K) the number of Bose systems which demonstrably pass into a condensate has considerably increased. These include several isotopes of alkali gas atoms as well as fermionic atoms that pair into integerspin (boson) composites. Although an ideal Bose gas does exhibit a low-temperature critical instability, the ideal BE gas theory is not, on its own, able to describe the BE condensate wave state. In order for a theory of bosons to account for a condensate wave state, interactions between the bosons must be included. Nevertheless, considerable interesting physics is contained in the ideal Bose gas model.