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The central topic of this letter is to show that light-matter hybridization not only gives rise to novel dynamic responses but can also modify intermolecular interactions and induce new structural order. Using the van der Waals (vdW) system in an optical cavity as an example, we predict the effects of interference and collectivity in cavity-induced many-body dispersion interactions. Specifically, the leading order correction due to cavity-induced quantum fluctuations leads to 3-body and 4-body vdW interactions, which can align intermolecular vectors and are not pairwise additive. In addition, the cavity-induced dipole leads to a single-molecule energy shift that aligns individual molecules, and a pair-wise interaction that scales as $R^{-3}$ instead of the standard $R^{-6}$ distance scaling. The coefficients of all these cavity-induced corrections depend on the cavity frequency and are renormalized by the effective Rabi frequency, which in turn depends on the particle density. Finally, we study the interaction of the vdW system in a cavity with an external object and find a significant enhancement in the interaction range due to modified distance scaling laws. These theoretical predictions suggest the possibility of cavity-induced nematic or smectic order and may provide an essential clue to understanding intriguing phenomena observed in optical cavities, such as strongly-modified ground-state reactivity, ion transport and solvent polarity.

The development of computational resources has made it possible to determine upper bounds for atomic and molecular energies with high precision. Yet, error bounds to the computed energies have been available only as estimates. In this paper, the Pollak-Martinazzo lower-bound theory, in conjunction with correlated Gaussian basis sets, is elaborated and implemented to provide sub-parts-per-million convergence of the ground- and excited-state energies for the He, Li, and Be atoms. The quality of the lower bounds is comparable to that of the upper bounds obtained from the Ritz method. These results exemplify the power of lower bounds to provide tight estimates of atomic energies.

In this work, our purpose is to show how the symmetry of identical particles can influence the time evolution of free particles in the nonrelativistic and relativistic domains. For this goal, we consider a system of either two distinguishable or indistinguishable (bosons and fermions) particles. Two classes of initial conditions have been studied: different initial locations with the same momenta, and the same locations with different momenta. The flight time distribution of particles arriving at a `screen' is calculated in each case. Fermions display broader distributions as compared with either distinguishable particles or bosons, leading to earlier and later arrivals for all the cases analyzed here. The symmetry of the wave function seems to speed up or slow down propagation of particles. Due to the cross terms, certain initial conditions lead to bimodality in the fermionic case. Within the nonrelativistic domain and when the short-time survival probability is analyzed, if the cross term becomes important, one finds that the decay of the overlap of fermions is faster than for distinguishable particles which in turn is faster than for bosons. These results are of interest in the short time limit since they imply that the well-known quantum Zeno effect would be stronger for bosons than for fermions.Fermions also arrive earlier than bosons when they are scattered by a delta barrier. Furthermore, the particle symmetry does not affect the mean tunneling flight time and it is given by the phase time for the distinguishable particle., Comment: 25 pages, 1 table, 5 figures

Quantum reflection of thermal He atoms from various surfaces (glass slide, GaAs wafer, flat and structured Cr) at grazing conditions is studied within the elastic close-coupling formalism. Comparison with the experimental results of B.S. Zhao et al, Phys. Rev. Lett. {\bf 105}, 133203 (2010) is quite reasonable but the conclusions of the present theoretical analysis are different from those discussed in the experimental work. The universal linear behavior observed in the dependence of the reflection probability on the incident wave vector component perpendicular to the surface is only valid at small values of the component whereas, at larger values, deviation from the linearity is evident, approaching a quadratic dependence at higher values. The surface roughness seems to play no important role in this scattering. Moreover, the claim that one observes a transition from quantum to classical reflection seems to be imprecise., Comment: 15 pages, 4 figures, 1 table. arXiv admin note: text overlap with arXiv:1807.06985

Time averaging of weak values using the quantum transition path time probability distribution enables us to establish a general uncertainty principle for the weak values of two not necessarily Hermitian operators. This new principle is a weak value analog of the Heisenberg-Robertson strong value uncertainty principle. It leads to the conclusion that it is possible to determine with high accuracy the simultaneous mean weak values of non-commuting operators by judicious choice of the pre- and post-selected states. Generally, when the time fluctuations of the two weak values are proportional to each other there is no uncertainty limitation on their variances and, in principle, their means can be determined with arbitrary precision even though their corresponding operators do not commute. To exemplify these properties we consider specific weak value uncertainty relations for the time-energy, coordinate-momentum and coordinate-kinetic energy pairs. In addition we analyze spin operators and the Stern-Gerlach experiment in weak and strong inhomogeneous magnetic fields. This classic case leads to anomalous spin values when the field is weak. However, anomalous spin values are also associated with large variances implying that their measurement demands increased signal averaging. These examples establish the importance of considering the time dependence of weak values in time of flight scattering experiments., Comment: 32 pages, 6 Figures

Using the quantum transition path time probability distribution we show that time averaging of weak values leads to unexpected results. We prove a weak value time energy uncertainty principle and time energy commutation relation. We also find that time averaging allows one to predict in advance the momentum of a particle at a post selected point in space with accuracy greater than the limit of $\hbar /2$ as dictated by the uncertainty principle. This comes at a cost - it is not possible at the same time to predict when the particle will arrive at the post selected point. A specific example is provided for one dimensional scattering from a square barrier., Comment: 14 pages, 2 figures

Weak values have been shown to be helpful especially when considering them as the outcomes of weak measurements. In this paper we show that in principle, the real and imaginary parts of the weak value of any operator may be elucidated from expectation values of suitably defined density, flux and hermitian commutator operators. Expectation values are the outcomes of strong (projective) measurements implying that weak values are general properties of operators in association with pre- and post-selection and they need not be preferentially associated with weak measurements. They should be considered as an important measurable property which provides added information as compared with the "standard" diagonal expectation value of an operator. As a first specific example we consider the determination of the real and imaginary parts of the weak value of the momentum operator employing projective time of flight experiments. Then the results are analyzed from the point of view of Bohmian mechanics. Finally we consider recent neutron interferometry experiments used to determine the weak values of the neutron spin., Comment: Accepted version

Quantum threshold reflection is a well known quantum phenomenon which prescribes that at threshold, except for special circumstances, a quantum particle scattering from any potential, even if attractive at long range, will be reflected with unit probability. In the past, this property has been associated with the so-called badlands region of the potential, where the semiclassical description of the scattering fails due to a rapid spatial variation of the deBroglie wavelength. This badlands region occurs far from the strong interaction region of the potential and has therefore been used to "explain" the quantum reflection phenomenon. In this paper, we show that the badlands region of the interaction potential is immaterial. The extremely long wavelength of the scattered particle at threshold is much longer than the spatial extension of the badlands region which therefore does not affect the scattering. For this purpose, we review the general proof for the existence of quantum threshold reflection to stress that it is only a consequence of continuity and boundary conditions. The nonlocal character of the scattering implies that the whole interaction potential is involved in the phenomenon. We then provide a detailed numerical study of the threshold scattering of a particle by a Morse potential especially in the time domain. We compare exact quantum computations with incoherent results obtained from a classical Wigner approximation. This study shows that close to threshold the time dependent amplitude of the scattered particle is negligible in the badlands region and that the mean flight time of the particle is not shortened due to a local reflection from the badlands region. This study should serve to definitely rule out the badlands region as a qualitative guide to the properties of quantum threshold reflection., Comment: 23 pages, 5 figures and one table

A second order classical perturbation theory is developed and applied to elastic atom corrugated surface scattering. The resulting theory accounts for experimentally observed asymmetry in the final angular distributions. These include qualitative features, such as reduction of the asymmetry with increased incidence energy as well as asymmetry in the location of the rainbow peaks with respect to the specular scattering angle. The theory is especially applicable to "soft" corrugated potentials. Analytic expressions for the angular distribution are derived for the exponential repulsive and Morse potential models. The theory is implemented numerically to a simplified model of the scattering of an Ar atom from a LiF(100) surface.

The Kramers turnover problem, that is obtaining a uniform expression for the rate of escape of a particle over a barrier for any value of the external friction was solved in the eighties. Two formulations were given, one by Melnikov and Meshkov (MM) (J. Chem. Phys. 85, 1018 (1986)), which was based on a perturbation expansion for the motion of the particle in the presence of friction. The other, by Pollak, Grabert and Haenggi (PGH) (J. Chem. Phys. 91, 4073 (1989)), valid also for memory friction, was based on a perturbation expansion for the motion along the collective unstable normal mode of the particle. Both theories did not take into account the temperature dependence of the average energy loss to the bath. Increasing the bath temperature will reduce the average energy loss. In this paper, we analyse this effect, using a novel perturbation theory. We find that within the MM approach, the thermal energy gained from the bath diverges, the average energy gain becomes infinite, implying an essential failure of the theory. Within the PGH approach increasing the bath temperature reduces the average energy loss but only by a finite small amount, of the order of the inverse of the reduced barrier height. This then does not seriously affect the theory. Analysis and application for a cubic potential and Ohmic friction are presented., Comment: Journal of Chemical Physics, accepted

Gaussian approximations to the Boltzmann operator have proven themselves in recent years as useful tools for the study of the thermodynamic properties of rare gas clusters. They are, however, not necessarily correct at very low temperatures. In this article we introduce a first-order correction term to the frozen Gaussian imaginary time propagator and apply it to the argon trimer. Our findings show that the correction term provides objective access to the quality of the propagator's results and clearly defines the "best" Gaussian width parameter. The strength of the correction monitored as a function of the temperature indicates that the results of the Gaussian propagator become questionable below a certain temperature. The interesting thermodynamic transition from a bounded trimer to three body dissociation lies in the temperature range for which the Gaussian approximation is predicted to be accurate., Comment: 9 pages, 5 figures, 1 table, corrections in the list of refereces, minor modifications in the text, to be published in Chemical Physics

Semiclassical Gaussian approximations to the Boltzmann operator have become an important tool for the investigation of thermodynamic properties of clusters of atoms at low temperatures. Usually, numerically expensive thawed Gaussian variants are applied. In this article, we introduce a numerically much cheaper frozen Gaussian approximation to the imaginary time propagator with a width matrix especially suited for the dynamics of clusters. The quality of the results is comparable to that of thawed Gaussian methods based on the single-particle ansatz. We apply the method to the argon trimer and investigate the dissociation process of the cluster. The results clearly show a classical-like transition from a bounded moiety to three free particles at a temperature T ~ 20 K, whereas previous studies of the system were not able to resolve this transition. Quantum effects, i.e., differences with the purely classical case manifest themselves in the low-temperature behavior of the mean energy and specific heat as well as in a slight shift of the transition temperature. We also discuss the influence of an artificial confinement of the atoms usually introduced to converge numerical computations. The results show that restrictive confinements often implemented in studies of clusters can influence the thermodynamic properties drastically. This finding may have implications on other studies of atomic clusters., Comment: 10 pages, 4 figures, 1 tabular, minor changes in the text, to be published in the Journal of Chemical Physics

Typically one expects that when a heavy particle collides with a surface, the scattered angular distribution will follow classical mechanics. The heavy mass assures that the de Broglie wavelength of the incident particle in the direction of the propagation of the particle (the parallel direction) will be much shorter than the characteristic lattice length of the surface, thus leading to a classical description. Recent work on molecular interferometry has shown that by increasing the perpendicular coherence length, one may observe interference of very heavy species passing through a grating. Here we show, using quantum mechanical simulations, that the same effect will lead to quantum diffraction of heavy particles colliding with a surface. We find that the effect is robust with respect to the incident energy, the angle of incidence and the mass of the particle. It may also be used to verify the quantum nature of the surface and its fluctuations at very low temperatures., Comment: 9 pages, 3 figures

Usually one finds that dissipation tends to make a quantum system more classical in nature. In this paper we study the effect of momentum dissipation on a quantum system. The momentum of the particle is coupled bilinearly to the momenta of a harmonic oscillator heat bath. For a harmonic oscillator system we find that the position and momentum variances for momentum coupling are respectively identical to momentum and position variances for spatial friction. This implies that momentum coupling leads to an increase in the fluctuations in position as the temperature is lowered, exactly the opposite of the classical like localization of the oscillator, found with spatial friction. For a parabolic barrier, momentum coupling causes an {\it increase} in the unstable normal mode barrier frequency, as compared to the lowering of the barrier frequency in the presence of purely spatial coupling. This increase in the frequency leads to an enhancement of the thermal tunneling flux, which below the crossover temperature becomes exponentially large. The crossover temperature between tunneling and thermal activation {\it increases} with momentum friction so that quantum effects in the escape are relevant at higher temperatures., Comment: 4 figures, to appear in Phys. Rev. E

A formula of Doetsch ({\em Math. Zeitschr.} {\bf 42}, 263 (1937)) is generalized and used to numerically invert the one-sided Laplace transform ${\hat C}(\beta)$. The necessary input is only the values of ${\hat C}(\beta)$ on the positive real axis. The method is applicable provided that the functions $\hat{C}(\beta)$ belong to the function space $L^2_\alpha$ defined by the condition that $ G(x) = e^{x\alpha}\hat{C}(e^x),~ \alpha > 0$ has to be square integrable. This space includes sums of exponential decays ${\hat C}(\beta)=\sum_n^{\infty}a_n e^{-\beta E_n}$, e.g. partition functions with $a_n = 1$. In practice, the inversion algorithm consists of two subsequent fast Fourier transforms. High accuracy inverted data can be obtained, provided that the signal is also highly accurate. The method is demonstrated for a harmonic partition function and resonant transmission through a barrier. We find accurately inverted functions even in the presence of noise., Comment: 13 figures