as quantum engineering. In the past two decades it has become increasingly clear that many (perhaps all) of the symptoms of classicality can be induced in quantum systems by their environments. Thus decoherence is caused by the interaction in which the environment in effect monitors certain observables of the system, destroying coherence between the pointer states corresponding to their eigenvalues. This leads to environment-induced superselection or einselection, a quantum process associated with selective loss of information. Einselected pointer states are stable. They can retain correlations with the rest of the universe in spite of the environment. Einselection enforces classicality by imposing an effective ban on the vast majority of the Hilbert space, eliminating especially the flagrantly nonlocal ''Schrodinger-cat states.'' The classical structure of phase space emerges from the quantum Hilbert space in the appropriate macroscopic limit. Combination of einselection with dynamics leads to the idealizations of a point and of a classical trajectory. In measurements, einselection replaces quantum entanglement between the apparatus and the measured system with the classical correlation. Only the preferred pointer observable of the apparatus can store information that has predictive power. When the measured quantum system is microscopic and isolated, this restriction on the predictive utility of its correlations with the macroscopic apparatus results in the effective ''collapse of the wave packet.'' The existential interpretation implied by einselection regards observers as open quantum systems, distinguished only by their ability to acquire, store, and process information. Spreading of the correlations with the effectively classical pointer states throughout the environment allows one to understand ''classical reality'' as a property based on the relatively objective existence of the einselected states. Effectively classical pointer states can be ''found out'' without being re-prepared, e.g, by intercepting the information already present in the environment. The redundancy of the records of pointer states in the environment (which can be thought of as their ''fitness'' in the Darwinian sense) is a measure of their classicality. A new symmetry appears in this setting. Environment-assisted invariance or envariance sheds new light on the nature of ignorance of the state of the system due to quantum correlations with the environment and leads to Born's rules and to reduced density matrices, ultimately justifying basic principles of the program of decoherence and einselection.

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Decoherence, einselection, and the quantum origins of the classical

In the last decade, ab initio simulations and especially Car-Parrinello molecular dynamics have significantly contributed to the improvement of our understanding of both the physical and chemical properties of water, ice, and hydrogen-bonded systems in general. At the heart of this family of in silico techniques lies the crucial idea of computing the many-body interactions by solving the electronic structure problem "on the fly" as the simulation proceeds, which circumvents the need for pre-parameterized potential models. In particular, the field of proton transfer in hydrogen-bonded networks greatly benefits from these technical advances. Here, several systems of seemingly quite different nature and of increasing complexity, such as Grotthuss diffusion in water, excited-state proton-transfer in solution, phase transitions in ice, and protonated water networks in the membrane protein bacteriorhodopsin, are discussed in the realms of a unifying viewpoint.

Proton transfer 200 years after von Grotthuss: insights from ab initio simulations.

Numerous studies have identified large quantum mechanical effects in the dynamics of liquid water. In this paper, we suggest that these effects may have been overestimated due to the use of rigid water models and flexible models in which the intramolecular interactions were described using simple harmonic functions. To demonstrate this, we introduce a new simple point charge model for liquid water, q-TIP4P/F, in which the O-H stretches are described by Morse-type functions. We have parametrized this model to give the correct liquid structure, diffusion coefficient, and infrared absorption frequencies in quantum (path integral-based) simulations. The model also reproduces the experimental temperature variation of the liquid density and affords reasonable agreement with the experimental melting temperature of hexagonal ice at atmospheric pressure. By comparing classical and quantum simulations of the liquid, we find that quantum mechanical fluctuations increase the rates of translational diffusion and orientational relaxation in our model by a factor of around 1.15. This effect is much smaller than that observed in all previous simulations of empirical water models, which have found a quantum effect of at least 1.4 regardless of the quantum simulation method or the water model employed. The small quantum effect in our model is a result of two competing phenomena. Intermolecular zero point energy and tunneling effects destabilize the hydrogen-bonding network, leading to a less viscous liquid with a larger diffusion coefficient. However, this is offset by intramolecular zero point motion, which changes the average water monomer geometry resulting in a larger dipole moment, stronger intermolecular interactions, and a slower diffusion. We end by suggesting, on the basis of simulations of other potential energy models, that the small quantum effect we find in the diffusion coefficient is associated with the ability of our model to produce a single broad O-H stretching band in the infrared absorption spectrum.

Competing quantum effects in the dynamics of a flexible water model

Nuclear quantum effects influence the structure and dynamics of hydrogen-bonded systems, such as water, which impacts their observed properties with widely varying magnitudes. This review highlights the recent significant developments in the experiment, theory, and simulation of nuclear quantum effects in water. Novel experimental techniques, such as deep inelastic neutron scattering, now provide a detailed view of the role of nuclear quantum effects in water's properties. These have been combined with theoretical developments such as the introduction of the principle of competing quantum effects that allows the subtle interplay of water's quantum effects and their manifestation in experimental observables to be explained. We discuss how this principle has recently been used to explain the apparent dichotomy in water's isotope effects, which can range from very large to almost nonexistent depending on the property and conditions. We then review the latest major developments in simulation algorithms and theory that have enabled the efficient inclusion of nuclear quantum effects in molecular simulations, permitting their combination with on-the-fly evaluation of the potential energy surface using electronic structure theory. Finally, we identify current challenges and future opportunities in this area of research.

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Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges

Nonlinear electron dynamics in metal clusters

The time-of-flight spectra of the neutron Compton scattering of solid palladium hydrides were measured at room temperature. This experiment, which was motivated by previous measurements on liquid H ...

Anomalous neutron Compton scattering in metallic hydrides: new experiments

Inelastic neutron scattering study of water in the subcritical and supercritical region

In a recent paper by Blostein et al. (Physica B 304 (2001) 357) was presented a critical theoretical analysis of different procedures, with which data of deep inelastic neutron scattering (DINS) experiments are usually processed. One part of that criticism—which is experimentally tested in the present paper—claimed the existence of serious errors in the determined areas of overlapping DINS-peaks, in particular in the case of the considerable overlapping of the strong proton peak with the weak deuteron peak. Our experimental test presented here consists in the comparison of the D-peak areas determined from DINS-data of H/D mixed systems, taken in both the “forward” and the “backward” scattering directions. Since there is no H-peak in the “backward” scattering direction, the claimed error cannot occur in this regime. New experimental results from (A) pure D2O, and (B) the equimolar H2O/D2O mixture, are presented. The liquids were contained in a Nb can. For both systems, it is shown that the D-peak areas in the “forward” and the “backward” scattering directions are essentially equal. This proves that the aforementioned criticism, although very stimulating, is of no relevance in the specific context of our (previous and present) DINS experiments. Moreover, the new experiments show that the cross-section of D is fully consistent with conventional expectations.

J. Mayers

Papers

Anomalous neutron Compton scattering in metallic hydrides: new experiments

Inelastic neutron scattering study of water in the subcritical and supercritical region

Experimental test of a theoretical analysis of deep inelastic neutron scattering experiments for H and D nuclei

Measurement of proton momentum distributions by eV neutron scattering

Density evolution of the kinetic energy of fluid and solid 4He at T=6.1 K.