Recent experiments have shown that fullerene and fluorofullerene molecules can produce interference patterns. These molecules have both rotational and vibrational degrees of freedom. This leads one to ask whether these internal motions can play a role in degrading the interference pattern. We study this by means of a simple model. Our molecule consists of two masses a fixed distance apart. It scatters from a potential with two or several peaks, thereby mimicking two or several slit interference. We find that in some parameter regimes the entanglement between the internal states and the translational degrees of freedom produced by the potential can decrease the visibility of the interference pattern. In particular, different internal states correspond to different outgoing wave vectors, so that if several internal states are excited, the total interference pattern will be the sum of a number of patterns, each with a different periodicity. The overall pattern is consequently smeared out. In the case of two different peaks, the scattering from the different peaks will excite different internal states so that the path the molecule takes become entangled with its internal state. This will also lead to degradation of the interference pattern. How these mechanisms might lead to the emergence of classical behavior is discussed.
We demonstrate two-photon interference using two remote single molecules as bright solid-state sources of indistinguishable photons. By varying the transition frequency and spectral width of one molecule, we tune and explore the effect of photon distinguishability. We discuss future improvements on the brightness of single-photon beams, their integration by large numbers on chips, and the extension of our experimental scheme to coupling and entanglement of distant molecules.
Molecular matter-wave interferometry enables novel strategies for manipulating the internal mechanical motion of complex molecules. Here, we show how chiral molecules can be prepared in a quantum superposition of two enantiomers by far-field matter-wave diffraction and how the resulting tunnelling dynamics can be observed. We determine the impact of ro-vibrational phase averaging and propose a setup for sensing enantiomer-dependent forces, parity-violating weak interactions, and environment-induced superselection of handedness, as suggested to resolve Hund's paradox. Using ab-initio tunnelling…
With a microwave-regime cyclic three-state configuration, an enantiomer-selective state transfer~(ESST) is carried out through the two-path interference between a direct one-photon coupling and an effective two-photon coupling. The $π$-phase difference in the one-photon process between two enantiomers makes the interference constructive for one enantiomer but destructive for the other. Therefore only one enantiomer is excited into a higher rotational state while the other remains in the ground state. The scheme is of flexibility in the pulse waveforms and the time order of two paths. We simula…
Under certain conditions an electron bound in a fast projectile-ion, colliding with a molecule, interacts mainly with the nuclei and inner shell electrons of atoms forming the molecule. Due to their compact localization in space and distinct separation from each other these molecular centers play in such collisions a role similar to that of optical slits in light scattering leading to pronounced interference in the spectra of the electron emitted from the projectile.
Scalability and miniaturization are hallmarks of solid-state platforms for photonic quantum technologies. Still a main challenge is two-photon interference from distinct emitters on chip. This requires local tuning, integration and novel approaches to understand and tame noise processes. A promising platform is that of molecular single photon sources. Thousands of molecules with optically tuneable emission frequency can be easily isolated in solid matrices and triggered with pulsed excitation. We here discuss Hong-Ou-Mandel interference experiments using several couples of molecules within few…
Destructive quantum interference (DQI) and its effects on electron transport is studied in chemical molecules and finite physical lattices that can be described by a discrete Hamiltonian. Starting from a bipartite system whose conductance zeros are known to exist between any two points of a specially designated set, the interference set, we use the Dyson equation to develop a general algorithm of determining the zero conductance points in complex systems, which are not necessarily bipartite. We illustrate this procedure as it applies to the fulvene molecule. The stability of the conductance ze…
A model multilevel molecule described by two sets of rotational internal energy levels of different parity and degenerate ground states, coupled by a constant interaction, is considered, by assuming that the random collisions in a gas of identical molecules, provoke transitions between adjacent energy levels of the same parity. The prescriptions of the continuous time quantum random walk are applied to the single molecule, interpreted as an open quantum system, and the master equation driving its internal dynamics is built for a general distribution of the waiting times between two consecutive…
We show that two-particle interferences can be used to probe the nuclear motion in a doubly-excited hydrogen molecule. The dissociation of molecular hydrogen by electron impact involves several decay channels, associated to different molecular rotational states, which produce quantum interferences in the detection of the atomic fragments. Thanks to the correlations between the angular momentum and vibrational states of the molecule, the fragments arising from each dissociation channel carry out a phase-shift which is a signature of the molecule rotation. These phase-shifts, which cannot be obs…
We review recent progress and future prospects of matter wave interferometry with complex organic molecules and inorganic clusters. Three variants of a near-field interference effect, based on diffraction by material nanostructures, at optical phase gratings, and at ionizing laser fields are considered. We discuss the theoretical concepts underlying these experiments and the experimental challenges. This includes optimizing interferometer designs as well as understanding the role of decoherence. The high sensitivity of matter wave interference experiments to external perturbations is demonstra…
The wave-particle duality of massive objects is a cornerstone of quantum physics and a key property of many modern tools such as electron microscopy, neutron diffraction or atom interferometry. Here we report on the first experimental demonstration of quantum interference lithography with complex molecules. Molecular matter-wave interference patterns are deposited onto a reconstructed Si(111) 7x7 surface and imaged using scanning tunneling microscopy. Thereby both the particle and the quantum wave character of the molecules can be visualized in one and the same image. This new approach to nano…
We present a rigorous study of vibrational relaxation in p-H2 + p-H2 collisions at cold and ultracold temperatures and identify an efficient mechanism of ro-vibrational energy transfer. If the colliding molecules are in different rotational and vibrational levels, the internal energy may be transferred between the molecules through an extremely state-selective process involving simultaneous conservation of internal energy and total rotational angular momentum. The same transition in collisions of distinguishable molecules corresponds to the rotational energy transfer from one vibrational state…
By using the zero-phonon line emission of an individual organic molecule, we realized a source of indistinguishable single photons in the near infrared. A Hong-Ou-Mandel interference experiment is performed and a two-photon coalescence probability of higher than 50% at 2 K is obtained. The contribution of the temperature-dependent dephasing processes to the two-photon interference contrast is studied. We show that the molecule delivers nearly ideal indistinguishable single photons at the lowest temperatures when the dephasing is nearly lifetime limited. This source is used to generate post-sel…
Integrated photonic circuits offer a promising route for studying coherent cooperative effects of a controlled collection of quantum emitters. However, spectral inhomogeneities, decoherence and material incompatibilities in the solid state make this a nontrivial task. Here, we demonstrate efficient coupling of a pair of organic molecules embedded in a plastic film to a TiO$_2$ microdisc resonator on a glass chip. Moreover, we tune the resonance frequencies of the molecules with respect to that of the microresonator by employing nanofabricated electrodes. For two molecules separated by a distan…
The observation of interference patterns in double-slit experiments with massive particles is generally regarded as the ultimate demonstration of the quantum nature of these objects. Such matter-wave interference has been observed for electrons, neutrons, atoms and molecules and it differs from classical wave-physics in that it can even be observed when single particles arrive at the detector one by one. The build-up of such patterns in experiments with electrons has been described as the "most beautiful experiment in physics". Here we show how a combination of nanofabrication and nanoimaging …
We discuss the optical response of a quantum molecule under the action of two lasers fields. Using a realistic model and parameters, we map the physical conditions to find three different phenomena reported in the literature: the tunneling induced transparency, the formation of Autler-Townes doublets, and the creation of a Mollow-like triplet. We found that the electron tunneling between quantum dots is the responsible for the different optical regime. Our results not only explain the experimental results in the literature but also give insights for future experiments and applications in optic…
We investigate the influence of intense, elliptically polarized driving fields on high-order harmonic spectra from aligned diatomic molecules. We derive a generalized two-center interference condition for elliptically polarized fields, which accounts for s-p mixing and the orbital symmetry, within the strong-field and the single-active electron approximation. We show that the non-vanishing ellipticity introduces an effective dynamic shift in the angle for which the two-center interference maxima and minima occur, with regard to the existing condition for linearly polarized fields. This shift d…
We study the magnetic relaxation rate Gamma of the single-molecule magnet Mn_{12}-tBuAc as a function of magnetic field component H_T transverse to the molecule's easy axis. When the spin is near a magnetic quantum tunneling resonance, we find that Gamma increases abruptly at certain values of H_T. These increases are observed just beyond values of H_T at which a geometric-phase interference effect suppresses tunneling between two excited energy levels. The effect is washed out by rotating H_T away from the spin's hard axis, thereby suppressing the interference effect. Detailed numerical calcu…
We present a proposal for controlling the conversion of ultracold atoms into molecules by fixing the phase difference between two oscillating magnetic fields. The scheme is based on the use of a magnetic Feshbach resonance with a field modulation that incorporates terms oscillating with frequencies corresponding to the main resonance and one of the subharmonics. The interference between the two association processes activated by the oscillating terms is controlled via the phase difference. As a result, significant increase or decrease of the effective interaction strength can be achieved. The …
We establish that matter-wave interference at near-resonant ultraviolet optical gratings can be used to spatially separate individual conformers of complex molecules. Our calculations show that the conformational purity of the prepared beam can be close to 100% and that all molecules remain in their electronic ground state. The proposed technique is independent of the dipole moment and the spin of the molecule and thus paves the way for structure-sensitive experiments with hydrocarbons and biomolecules, such as neurotransmitters and hormones, which evaded conformer-pure isolation so far
Interferometry of single particles with internal degrees of freedom is investigated. We discuss the interference patterns obtained when an internal state evolution device is inserted into one or both the paths of the interferometer. The interference pattern obtained is not uniquely determined by the completely positive maps (CPMs) that describe how the devices evolve the internal state of a particle. By using the concept of gluing of CPMs, we investigate the structure of all possible interference patterns obtainable for given trace preserving internal state CPMs. We discuss what can be inferre…
The subtle and fundamental issue of indistinguishability and interference between independent pathways to the same target state is examined in the context of coherent control of atomic and molecular processes, with emphasis placed on possible "which-way" information due to quantum entanglement established in the quantum dynamics. Because quantum interference between independent pathways to the same target state occurs only when the independent pathways are indistinguishable, it is first shown that creating useful coherence (as defined in the paper) between nondegenerate states of a molecule fo…
Polyatomic molecular ions contain many desirable attributes of a useful quantum system, including rich internal degrees of freedom and highly controllable coupling to the environment. To date, the vast majority of state-specific experimental work on molecular ions has concentrated on diatomic species. The ability to prepare and readout polyatomic molecules in single quantum states would enable diverse experimental avenues not available with diatomics, including new applications in precision measurement, sensitive chemical and chiral analysis at the single molecule level, and precise studies of…
We study the effect of atom-molecule internal tunneling on the ground state of atom-molecule Bose-Einstein condensates in a double-well potential. In the absence of internal tunneling between atomic and molecular states, the ground state is symmetric, which has equal-particle populations in two wells. From the linear stability analysis, we show that the symmetric stationary state becomes dynamically unstable at a certain value of the atom-molecule internal tunneling strength. Above the critical value of the internal tunneling strength, the ground state bifurcates to the particle-localized grou…
The realization of self-assembled molecular-electronic films, whose room-temperature transport properties are controlled by quantum interference (QI), is an essential step in the scale-up QI effects from single molecules to parallel arrays of molecules. Recently, the effect of destructive QI (DQI) on the electrical conductance of self-assembled monolayers (SAMs) has been investigated. Here, through a combined experimental and theoretical investigation, we demonstrate chemical control of different forms of constructive QI (CQI) in cross-plane transport through SAMs and assess its influence on c…
For a particle travelling through an interferometer, the trade-off between the available which-way information and the interference visibility provides a lucid manifestation of the quantum mechanical wave-particle duality. Here we analyze this relation for a particle possessing an internal degree of freedom such as spin. We quantify the trade-off with a general inequality that paints an unexpectedly intricate picture of wave-particle duality when internal states are involved. Strikingly, in some instances which-way information becomes erased by introducing classical uncertainty in the internal…
We address the influence of the molecular orbital geometry and of the molecular alignment with respect to the laser-field polarization on laser-induced nonsequential double ionization of diatomic molecules for different molecular species, namely $\mathrm{N}_2$ and $\mathrm{Li}_2$. We focus on the recollision excitation with subsequent tunneling ionization (RESI) mechanism, in which the first electron, upon return, promotes the second electron to an excited state, from where it subsequently tunnels. We show that the electron-momentum distributions exhibit interference maxima and minima due to t…
The possibility of quantum interference of a composite object with many internal degrees of freedom is studied, such that the internal degrees play a role of an internal environment. In particular, if the internal degrees have a capacity for an irreversible record of which-path information, then the internal-environment induced decoherence prevents external experimentalists from observing interference. Interference can be observed only if the interfering object is sufficiently isolated from the external environment, so that the object cannot record which-path information. Extrapolation to a hy…
Berry phase effects in spin systems lead to the suppression of tunneling effects when different tunneling paths interfere destructively. Such effects have been seen in several single-molecule magnets (SMMs) through measurements of magnetization dynamics, where the experimental signal may arise from the contributions of numerous energy levels. Here we present experimental measurements of Berry phase interference effects that are determined through electron-spin resonance on a four-fold symmetric SMM. Specifically, we measure transitions between tunnel-split excited states in the Ni$_4$ SMM in t…
Interference of more and more massive objects provides a spectacular confirmation of quantum theory. It is usually regarded as support for "wave-particle duality" and in an extension of this duality even as support for "complementarity". We first give an outline of the historical development of these notions. Already here it becomes evident that they are hard to define rigorously, i.e. have mainly a heuristic function. Then we discuss recent interference experiments of large and complex molecules which seem to support this heuristic function of "duality". However, we show that in these experim…
We predict that it is possible to cool rotational, vibrational and translational degrees of freedom of molecules by coupling a molecular dipole transition to an optical cavity. The dynamics is numerically simulated for a realistic set of experimental parameters using OH molecules. The results show that the translational motion is cooled to few $μ$K and the internal state is prepared in one of the two ground states of the two decoupled rotational ladders in few seconds. Shorter cooling times are expected for molecules with larger polarizability.
A book chapter where a new matrix function of the HMO Hamiltonian is proposed to deal with the Quantum Interference phenomenon in conjugated organic molecules.
We analyze two-center interference effects in the yields of ionization of a dissociating hydrogen molecular ion by an ultrashort VUV laser pulse. To this end, we performed numerical simulations of the time-dependent Schrödinger equation for a H$_2^+$ model ion interacting with two time-delayed laser pulses. The scenario considered corresponds to a pump-probe scheme, in which the first (pump) pulse excites the molecular ion to the first excited dissociative state and the second (probe) pulse ionizes the electron as the ion dissociates. The results of our numerical simulations for the ionization…
Since the work of Anderson on localization, interference effects for the propagation of a wave in the presence of disorder have been extensively studied, as exemplified in coherent backscattering (CBS) of light. In the multiple scattering of light by a disordered sample of thermal atoms, interference effects are usually washed out by the fast atomic motion. This is no longer true for cold atoms where CBS has recently been observed. However, the internal structure of the atoms strongly influences the interference properties. In this paper, we consider light scattering by an atomic dipole transi…
We perform a phase-space analysis of strong-field enhanced ionisation in molecules, with emphasis on quantum-interference effects. Using Wigner quasi-probability distributions and the quantum Liouville equation, we show that the momentum gates reported in a previous publication [N. Takemoto and A. Becker, Phys. Rev. A \textbf{84}, 023401 (2011)] may occur for static driving fields, and even for no external field at all. Their primary cause is an interference-induced bridging mechanism that occurs if both wells in the molecule are populated. In the phase-space regions for which quantum bridges …
We investigate direct above-threshold ionization in diatomic molecules, with particular emphasis on how quantum interference is altered by a driving field of non-vanishing ellipticity. This interference may be either temporal, i.e., related to ionization events occurring at different times, or spatial, i.e., related to the electron emission at different centers in the molecule. Employing the strong-field approximation and saddle-point methods, we find that, in general, for non-vanishing ellipticity, there will be a blurring of the temporal and spatial interference patterns. The former blurring…
The phenomenon of "overlapping resonances interference-induced transparency" (ORIT) is introduced and studied in detail for the $S_0 \to S_2/S_1$ photoexcitation of cold pyrazine (C$_4$H$_4$N$_2$). In ORIT a molecule becomes transparent at specific wavelengths due to interferences between envelopes of spectral lines displaying overlapping resonances. An example is the $S_2\leftrightarrow S_1$ internal conversion in pyrazine where destructive interference between overlapping resonances causes the $S_0 \to S_2/S_1$ light absorption to disappear at certain wavelengths. ORIT may be of practical im…
We investigate theoretically the dissociative ionization of a H2+ molecule using two ultrashort laser (pump-probe) pulses. The pump pulse prepares a dissociating nuclear wave packet on an ungerade surface of H2+. Next, an UV (or XUV) probe pulse ionizes this dissociating state at large (R = 20 - 100 bohr) internuclear distance. We calculate the momenta distributions of protons and photoelectrons which show a (two-slit-like) interference structure. A general, simple interference formula is obtained which depends on the electron and protons momenta, as well as on the pump-probe delay on the puls…
A pair of coherent femtosecond pulse excitations applied to a molecule with strong electron-phonon coupling creates a coherent superposition of a low momentum and a high momentum wavepacket in the vibrational states of both the excited state and the ground state of the coherent transition. As the excited state is accelerated further, interference between the high momentum ground state contribution and the low momentum excited state contribution causes a photon echo. This photon echo is a direct consequence of quantum interference between separate vibrational trajectories and can therefore prov…
We study the non-equiliribium dynamics of atom-molecule Bose gases in a double-well potential. In this system, the internal atom-molecule tunneling has significant influence on the dynamics. We investigate the periodicity of dynamics by studying the level statistics of the quantum system. We find that chaotic energy eigenstates arise from the competition between the interwell and the atom-molecule internal tunnelings. Furthermore, we show that the physical quantities relax to the microcanonical averages in the full-quantum dynamics when the system is chaotic. This thermalization is caused by t…
The de Broglie wave nature of matter is a paradigmatic example of fundamental quantum physics and enables precise measurements of forces, fundamental constants and even material properties. However, even though matter-wave interferometry is nowadays routinely realized in many laboratories, this feat has remained an outstanding challenge for the vast class of native polypeptides, the building blocks of life, which are ubiquitous in biology but fragile and difficult to handle. Here, we demonstrate the quantum wave nature of gramicidin, a natural antibiotic composed of 15 amino acids. Femtosecond…
We analyze theoretically the interplay between the torsional and the rotational motion of an aligned biphenyl-like molecule. To do so, we consider a transition between two electronic states with different internal torsional potentials, induced by means of a resonant laser pulse. The change in the internal torsional potential provokes the motion of the torsional wavepacket in the excited electronic state, modifying the structure of the molecule, and hence, its inertia tensor. We find that this process has a strong impact on the rotational wave function, displaying different behavior depending o…
Controlling the internal degrees of freedom is a key challenge for applications of cold and ultracold molecules. Here, we demonstrate rotational-state cooling of trapped methyl fluoride molecules (CH3F) by optically pumping the population of 16 M-sublevels in the rotational states J=3,4,5, and 6 into a single level. By combining rotational-state cooling with motional cooling, we increase the relative number of molecules in the state J=4, K=3, M=4 from a few percent to over 70%, thereby generating a translationally cold (~30mK) and nearly pure state ensemble of about 10^6 molecules. Our scheme …
We theoretically investigate up-conversion process of entangled two photons on a dimer molecule, which is coupled by a cavity or nanoscale metallic structure. Within one-dimensional input-output theory, the propagators of the photons are derived analytically and the up-conversion probability is calculated numerically. It is shown that the coupling with the nanostructure clearly enhances the process. We also find that the enhancement becomes further pronounced for some balanced system parameters such as the quantum correlation between photons, radiation decay rates and coupling between the nano…
