Importance Of Quantum Effects Research Articles

Explaining the Efficiency of Photosynthesis: Quantum Uncertainty or Classical Vibrations?

Photosynthetic organisms are known to use a mechanism of vibrationally assisted exciton energy transfer to efficiently harvest energy from light. The importance of quantum effects in this mechanism is a long-standing topic of debate, which has traditionally focused on the role of excitonic coherences. Here, we address another recent claim: that the efficient energy transfer in the Fenna–Matthews–Olson complex relies on nuclear quantum uncertainty and would not function if the vibrations were classical. We present a counter-example to this claim, showing by trajectory-based simulations that a description in terms of quantum electrons and classical nuclei is indeed sufficient to describe the funneling of energy to the reaction center. We analyze and compare these findings to previous classical-nuclear approximations that predicted the absence of an energy funnel and conclude that the key difference and the reason for the discrepancy is the ability of the trajectories to properly account for Newton’s third law.

Quantum effects in photosensitization: the case of singlet oxygen generation by thiothymines.

Photosensitization is the indirect electronic excitation of a molecule with the aid of a photosensitizer and is a bimolecular nonradiative energy transfer. In this study, we have attempted to elucidate its mechanism, and we do this by calculating rate constants of photosensitization of oxygen by thiothymines (2-thiothymine, 4-thiothymine and 2,4 dithiothymine). The rate constants have been calculated using two approaches: (a) a classical limit of Fermi's Golden Rule (FGR), and (b) a time-dependent variant of FGR, where the treatment is purely quantum mechanical. The former approach has previously been developed for bimolecular systems and has been applied to the photosensitization reactions studied here. The latter approach, however, has so far only been used for unimolecular reactions, and in this work, we describe how it can be adapted for bimolecular reactions. Experimentally, all three thiothymines are known to have significant singlet oxygen yields, which are indicative of similar rates. Rate constants calculated using the time-dependent variant of FGR are similar across all three thiothymines. While the classical approximation gives reasonable rate constants for 2-thiothymine, it severely underestimates them for 4-thiothymine and 2,4 dithiothymine, by several orders of magnitude. This work indicates the importance of quantum effects in driving photosensitization.

4s to 5s and 4p photoexcitation dynamics of K atoms from the surface of helium nanodroplets: a theoretical study

We study the photodissociation of the potassium atom from a superfluid helium nanodroplet upon 5s 2S or 4p 2P excitation using the time-dependent helium density functional method (He-TDDFT). The importance of quantum effects is assessed by comparing the absorption spectrum obtained for a classical or a quantum description of the K atom. In the case of the 5s 2S ← 4s 2S excitation the difference is rather large, and we use a quantum description for the ensuing direct dissociation dynamics. In the case of the 4p 2P ← 4s 2S absorption spectrum, the difference is much smaller, hence a classical description of K is used to describe 4p 2P excitation dynamics. Excitation to the 4p 2Σ1/2 state leads to the direct dissociation of the K atom, while the 4p 2Π3/2 state initially leads to the formation of an exciplex and the 4p 2Π1/2 state to a bouncing atom above the droplet surface. Remarkably, electronic relaxation can be observed for the latter two states, leading to spin-orbit relaxation and the binding of the initially departing one-atom excimer as a ring excimer for the 2P3/2 state and to the formation of a bound, ring excimer for the 2Π1/2 state.

Exotic spin phases in two-dimensional spin-orbit coupled models: Importance of quantum effects

We investigate the phase diagrams of the effective spin models derived from Fermi-Hubbard and Bose-Hubbard models with Rashba spin-orbit coupling, using string bond states, one of the quantum tensor network states methods. We focus on the role of quantum fluctuation effect in stabilizing the exotic spin phases in these models. For boson systems, and when the ratio between inter-particle and intra-particle interaction $\lambda > 1$, the out-of-plane ferromagnetic (FM) and antiferromagnetic (AFM) phases obtained from quantum simulations are the same to those obtained from classic model. However, the quantum order-by-disorder effect reduces the classical in-plane XY-FM and XY-vortex phases to the quantum X/Y-FM and X/Y-stripe phase when $\lambda < 1$. The spiral phase and skyrmion phase can be realized in the presence of quantum fluctuation. For the Fermi-Hubbard model, the quantum fluctuation energies are always important in the whole parameter regime. %, which are much larger than those of the Bose model. A general picture to understand the phase diagrams from symmetry point of view is also presented.

Revisiting Lepton Flavour Universality in B Decays

Lepton flavour universality (LFU) in B-decays is revisited by considering a class of semileptonic operators defined at a scale Λ above the electroweak scale v. The importance of quantum effects is emphasised [F. Feruglio, P. Paradisi and A. Pattori, arXiv:1606.00524 [hep-ph], to appear in PRL]. We construct the low-energy effective Lagrangian taking into account the running effects from Λ down to v through the one-loop renormalization group equations (RGE) in the limit of exact electroweak symmetry and QED RGEs from v down to the 1 GeV scale. The most important quantum effects turn out to be the modification of the leptonic couplings of the vector boson Z and the generation of a purely leptonic effective Lagrangian. Large LFU breaking effects in Z and τ decays as well as visible lepton flavour violating (LFV) effects in τ decays are induced.

Phase diagram and spin correlations of the Kitaev-Heisenberg model: Importance of quantum effects

We explore the phase diagram of the Kitaev-Heisenberg model with nearest neighbor interactions on the honeycomb lattice using the exact diagonalization of finite systems combined with the cluster mean field approximation, and supplemented by the insights from the linear spin-wave and second--order perturbation theories. This study confirms that by varying the balance between the Heisenberg and Kitaev term, frustrated exchange interactions stabilize in this model four phases with magnetic long range order: N\'eel phase, ferromagnetic phase, and two other phases with coexisting antiferromagnetic and ferromagnetic bonds, zigzag and stripy phases. They are separated by two disordered quantum spin-liquid phases, and the one with ferromagnetic Kitaev interactions has a substantially broader range of stability as the neighboring competing ordered phases, ferromagnetic and stripy, have very weak quantum fluctuations. Focusing on the quantum spin-liquid phases, we study spatial spin correlations and dynamic spin structure factor of the model by the exact diagonalization technique, and discuss the evolution of gapped low-energy spin response across the quantum phase transitions between the disordered spin liquid and magnetic phases with long range order.

Revisiting Lepton Flavor Universality in B Decays.

Lepton flavor universality (LFU) in B decays is revisited by considering a class of semileptonic operators defined at a scale Λ above the electroweak scale v. The importance of quantum effects, so far neglected in the literature, is emphasized. We construct the low-energy effective Lagrangian taking into account the running effects from Λ down to v through the one-loop renormalization group equations (RGEs) in the limit of exact electroweak symmetry and QED RGEs from v down to the 1GeV scale. The most important quantum effects turn out to be the modification of the leptonic couplings of the vector boson Z and the generation of a purely leptonic effective Lagrangian. Large LFU breaking effects in Z and τ decays and visible lepton flavor violating effects in the processes τ→μℓℓ, τ→μρ, τ→μπ, and τ→μη^{(')} are induced.

Modeling and designing micro- and nano-structured metamaterials: Towards the application of exotic behaviors

The lack of suitable computational methods has significantly restricted the creativity of engineers in designing the materials to be used in technological applications. When one wants exact analytical solutions for a given physical system, then usually drastic and restrictive simplifying assumptions are needed. In particular, homogeneity of physical and geometrical properties at lower length-scale is the standard assumption in continuum mechanics. On the other hand, it is well-known since the pioneering work of Gabrio Piola, and then re-established in the works by Mindlin, Toupin, Green, Adkins and Germain, that it is possible to synthetically describe microscopic inhomogeneity by means of field theories incorporating additional kinematical fields. The characteristic length-scale affecting macro-behavior can even be of the order of nanometers, in which case the intuition due to Richard Feynman about the importance of quantum effects at macro-scale could open the path to technological advancements. In the present paper we review some of the literature in the field and try to indicate some research perspectives that seem to us potentially ground-breaking. In particular, following the suggestion of Professor dell’Isola, we briefly describe his concept of pantographic lattices and sheets whose importance in nano-technology could be relevant.

Anisotropic planar Heisenberg model of the quantum heterobimetallic zigzag chains with bridged ReIV-CuIImagnetic complexes

An anisotropic quantum planar Heisenberg model is proposed and thoroughly analyzed within the numerical density-matrix renormalization group approach. The model takes into account the site-dependent alternating directions of the local coordination system for the Re${}^{\mathit{IV}}$ ions and both the axial and the rhombic single-ion anisotropy terms. Thermodynamic properties of a simpler collinear model without the rhombic term and its Ising counterpart as well as some previous approximations for Re${}^{\mathit{IV}}$-ion-containing compounds are discussed to point out the importance of quantum effects and deficiencies of classical approaches. For the noncollinear model with the alternating uniaxial local $z$ axis tilted by the angle $\ensuremath{\theta}$ from the global chain axis formed by copper ions, some symmetries for the single-crystal susceptibilities are found. In the strong-anisotropy limit some striking maxima in the corresponding single-crystal $\ensuremath{\chi}T$ products are revealed and their relation to the experimental determination of the anisotropy parameters is emphasized. Some cases to which the collinear model for zigzag chains is fully applicable are indicated. Finally, fitting the reference experimental data for a powder sample of given chloro- and cyanobridged zigzag chains, the weaker magnetic coupling and the uniaxial single-ion anisotropy term parameters have been found. The corrected value of the ferromagnetic interaction parameter implies that for the cyanobridge compound the record of the highest superexchange through cyanide has not been beaten.

Computer simulations of quantum tunnelling in enzyme-catalysed hydrogen transfer reactions

Transfer of hydrogen as a proton, hydride or hydrogen atom is an important step in many enzymic reactions. Experiments show kinetic isotope effects (KIEs) for some enzyme-catalysed hydrogen transfer reactions that deviate significantly from the limits imposed by considering the differences in mass of the isotopes alone (i.e. the semiclassical limit). These KIEs can be explained if the transfer of the hydrogen species occurs via a quantum mechanical tunnelling mechanism. The unusual temperature dependence of some KIEs has led to suggestions that enzymes have evolved to promote tunnelling through dynamics - a highly controversial hypothesis. Molecular simulations have a vital role in resolving these questions, providing a level of detail of analysis not possible through experiments alone. Here, we review computational molecular modelling studies of quantum tunnelling in enzymes, in particular focusing on the enzymes soybean lipoxygenase-1 (SLO-1), dihydrofolate reductase (DHFR), methylamine dehydrogenase (MADH) and aromatic amine dehydrogenase (AADH) to illustrate the current controversy regarding the importance of quantum effects in enzyme catalysis.

The OH + D2→ HOD + D angle–velocity distribution: quasi-classical trajectory calculations on the YZCL2 and WSLFH potential energy surfaces and comparison with experiments at ET = 0.28 eV

The angle-velocity distribution (HOD) of the OH + D(2) reaction at a relative translational energy of 0.28 eV has been calculated using the quasi-classical trajectory (QCT) method on the two most recent potential energy surfaces available (YZCL2 and WSLFH PESs), widely extending a previous investigation of our group. Comparison with the high resolution experiments of Davis and co-workers (Science, 2000, 290, 958) shows that the structures (peaks) found in the relative translational energy distributions of products could not be satisfactorily reproduced in the calculations, probably due to the classical nature of the QCT method and the importance of quantum effects. The calculations, however, worked quite well for other properties. Overall, both surfaces led to similar results, although the YZCL2 surface is more accurate to describe the H(3)O PES, as derived from comparison with high level ab initio results. The differences observed in the QCT calculations were interpreted considering the somewhat larger anisotropy of the YZCL2 PES when compared with the WSLFH PES.

Proton delocalization under extreme conditions of high pressure and temperature

Knowledge of the behaviour of light hydrogen-containing molecules under extreme conditions of high pressure and temperature is crucial to a comprehensive understanding of the fundamental physics and chemistry that is relevant under such conditions. It is also vital for interpreting the results of planetary observations, in particular those of the gas giants, and also for various materials science applications. On a fundamental level, increasing pressure causes the redistribution of the electronic density, which results in a modification of the interatomic potentials followed by a consequent qualitative change in the character of the associated bonding. Ultimately, at sufficiently high pressure, one may anticipate a transformation to a homogeneously bonded material possessing unusual physical properties (e.g. a quantum fluid). As temperature increases so does the concentration of ionised species leading ultimately to a plasma. Considerable improvements have recently been made in both the corresponding experimental and theoretical investigations. Here we review recent results for hydrogen and water that reveal unexpected routes of transformation to nonmolecular materials. We stress the importance of quantum effects, which remain significant even at high temperatures.

Quantum effects in liquid water from an ab initio-based polarizable force field

The importance of quantum effects as well as the accuracy of the ab initio-based polarizable TTM2.1-F force field in describing liquid water are quantitatively assessed by a detailed analysis of the temperature dependence of several thermodynamic and dynamical properties computed using the path-integral molecular dynamics and centroid molecular dynamics methods. The results show that quantum effects are not negligible even at relatively high temperatures, and their inclusion in simulations with the TTM2.1-F water model is necessary to achieve a more accurate description of the liquid properties. Comparison with the results reported in the literature for empirical, nonpolarizable force fields demonstrates that the effects of the nuclear quantization on the dielectric constant are dependent in part on how the electronic polarization is described in the underlying water model, while comparison with other ab initio-based force fields shows that the TTM2.1-F model provides an overall accurate description of liquid water. Analysis of the isotope effect on the dynamical properties does not display significant temperature dependence. This suggests that the contribution of quantum tunneling, which has been proposed as a possible cause for the different orientational dynamics observed for the HDO:H(2)O and HDO:D(2)O systems, appears to be small.

Dynamics of Electronic States and Spin−Flip for Photodissociation of Dihalogens in Matrices: Experiment and Semiclassical Surface-Hopping and Quantum Model Simulations for F2 and ClF in Solid Ar

Three approaches are combined to study the electronic states' dynamics in the photodissociation of F(2) and ClF in solid argon. These include (a) semiclassical surface-hopping simulations of the nonadiabatic processes involved. These simulations are carried out for the F(2) molecule in a slab of 255 argon atoms with periodic boundary conditions at the ends. The full manifold of 36 electronic states relevant to the process is included. (b) The second approach involves quantum mechanical reduced-dimensionality models for the initial processes induced by a pump laser pulse, which involve wavepacket propagation for the preoriented ClF in the frozen argon lattice and incorporate the important electronic states. The focus is on the study of quantum coherence effects. (c) The final approach is femtosecond laser pump-probe experiments for ClF in Ar. The combined results for the different systems shed light on general properties of the nonadiabatic processes involved, including the singlet to triplet and intertriplet transition dynamics. The main findings are (1) that the system remains in the initially excited-state only for a very brief, subpicosecond, time period. Thereafter, most of the population is transferred by nonadiabatic transitions to other states, with different time constants depending on the systems. (2) Another finding is that the dynamics is selective with regard to the electronic quantum numbers, including the Lambda and Omega quantum numbers, and the spin of the states. (3) The semiclassical simulations show that prior to the first "collision" of the photodissociated F atom with an Ar atom, the argon atoms can be held frozen, without affecting the process. This justifies the rigid-lattice reduced-dimensionality quantum model for a brief initial time interval. (4) Finally, degeneracies between triplets and singlets are fairly localized, but intertriplet degeneracies and near degeneracies can span an extensive range. The importance of quantum effects in photochemistry of matrix-isolated molecules is discussed in light of the results.

Product angular distribution for the H+CD4 abstraction reaction: The importance of quantum effects

Product angular distribution for the H+CD4 abstraction reaction: The importance of quantum effects

Storage of Hydrogen at 303 K in Graphite Slitlike Pores from Grand Canonical Monte Carlo Simulation

Grand canonical Monte Carlo (GCMC) simulations were used for the modeling of the hydrogen adsorption in idealized graphite slitlike pores. In all simulations, quantum effects were included through the Feynman and Hibbs second-order effective potential. The simulated surface excess isotherms of hydrogen were used for the determination of the total hydrogen storage, density of hydrogen in graphite slitlike pores, distribution of pore sizes and volumes, enthalpy of adsorption per mole, total surface area, total pore volume, and average pore size of pitch-based activated carbon fibers. Combining experimental results with simulations reveals that the density of hydrogen in graphite slitlike pores at 303 K does not exceed 0.014 g/cm(3), that is, 21% of the liquid-hydrogen density at the triple point. The optimal pore size for the storage of hydrogen at 303 K in the considered pore geometry depends on the pressure of storage. For lower storage pressures, p < 30MPa, the optimal pore width is equal to a 2.2 collision diameter of hydrogen (i.e., 0.65 nm), whereas, for p congruent with 50MPa, the pore width is equal to an approximately 7.2 collision diameter of hydrogen (i.e., 2.13 nm). For the wider pores, that is, the pore width exceeds a 7.2 collision diameter of hydrogen, the surface excess of hydrogen adsorption is constant. The importance of quantum effects is recognized in narrow graphite slitlike pores in the whole range of the hydrogen pressure as well as in wider ones at high pressures of bulk hydrogen. The enthalpies of adsorption per mole for the considered carbonaceous materials are practically constant with hydrogen loading and vary within the narrow range q(st) congruent with 7.28-7.85 kJ/mol. Our systematic study of hydrogen adsorption at 303 K in graphite slitlike pores gives deep insight into the timely problem of hydrogen storage as the most promising source of clean energy. The calculated maximum storage of hydrogen is equal to approximately 1.4 wt %, which is far from the United States Department of Energy (DOE) target (i.e., 6.5 wt %), thus concluding that the total storage amount of hydrogen obtained at 303 K in graphite slitlike pores of carbon fibers is not sufficient yet.

Hydrogen bonding and collective proton modes in clusters and periodic layers of squaric acid: A density functional study

Hydrogen bonding in clusters and extended layers of squaric acid molecules has been investigated by density functional computations. Equilibrium geometries, harmonic vibrational frequencies, and energy barriers for proton transfer along hydrogen bonds have been determined using the Car–Parrinello method. The results provide crucial parameters for a first principles modeling of the potential energy surface, and highlight the role of collective modes in the low-energy proton dynamics. The importance of quantum effects in condensed squaric acid systems has been investigated, and shown to be negligible for the lowest-energy collective proton modes. This information provides a quantitative basis for improved atomistic models of the order–disorder and displacive transitions undergone by squaric acid crystals as a function of temperature and pressure.

Harmonic Lattice Theory of Coulomb Solids and Comparison with Monte Carlo Simulations

The potential energy of the OCP in the fluid phase is known to great accuracy from Monte Carlo (MC) data obtained from very long simulations. For the crystalline phase, bcc or fcc, the MC simulations are equally accurate but can also be represented nearly analytically in the Harmonic Lattice (HL) approximation. We give here recent results for the anharmonic effects in the classical regime T ≫ Tp (where Tp is the on plasma temperature) both exact and obtained in the HL approximation. We also give results for the harmonic potential energy in a quantum OCP crystal and discuss the importance of quantum effects for the fluid-lattice phase transition.

Full dimensional quantum calculations of the CH4+H→CH3+H2 reaction rate

Accurate full-dimensional quantum mechanical calculations are reported for the CH4+H→CH3+H2 reaction employing the Jordan–Gilbert potential energy surface. Benchmark results for the thermal rate constant and the cumulative reaction probability are presented and compared to classical transition state theory as well as reduced dimensionality quantum scattering calculations. The importance of quantum effects in this system is highlighted.

Quantum Contribution to Gas Adsorption in Carbon Nanotubes

Recently published Monte Carlo simulation studies have demonstrated that carbon nanotubes could be a new adsorbent material for the storage of gases such as hydrogen. This engineering application suitable for the use of hydrogen in fuel cells has motivated much experimental and theoretical work, including the present work. Using grand canonical Monte Carlo simulations, we have calculated the amount of hydrogen adsorbed in various arrangements of single-walled carbon nanotubes at high pressure and room temperature. For these thermodynamic states, we determined the importance of quantum effects on hydrogen adsorption. These quantum corrections were computed following a perturbative scheme already used, for instance, in simulation studies of phase diagrams of water, neon and methane. Taking into account the quantum corrections, we estimated, for each considered arrangement, the most favorable diameter and relative distance of the nanotubes for hydrogen adsorption.