Transporting and concentrating vibrational energy to promote isomerization.

Visible-light absorption and transport of the resultant electronic excitations to a reaction centre through Förster resonance energy transfer1-3 (FRET) are critical to the operation of biological light-harvesting systems4, and are used in various artificial systems made of synthetic dyes5, polymers6 or nanodots7,8. The fundamental equations describing FRET are similar to those describing vibration-to-vibration (V-V) energy transfer9, and suggest that transport and localization of vibrational energy should, in principle, also be possible. Although it is known that vibrational excitation can promote reactions10-16, transporting and concentrating vibrational energy has not yet been reported. We have recently demonstrated orientational isomerization enabled by vibrational energy pooling in a CO adsorbate layer on a NaCl(100) surface17. Here we build on that work to show that the isomerization reaction proceeds more efficiently with a thick 12C16O overlayer that absorbs more mid-infrared photons and transports the resultant vibrational excitations by V-V energy transfer to a 13C18O-NaCl interface. The vibrational energy density achieved at the interface is 30 times higher than that obtained with direct excitation of the interfacial CO. We anticipate that with careful system design, these concepts could be used to drive other chemical transformations, providing new approaches to condensed phase chemistry.

Superconducting single-photon detectors in the mid-infrared for physical chemistry and spectroscopy.

Applications of vibrational spectroscopy throughout the field of physical chemistry are limited by detectors with poor temporal resolution, low detection efficiency, and high background levels. Up to now, the field has relied upon detectors based on semiconducting materials with small bandgaps, which unavoidably leads to a compromise between good spectral response and noise at long wavelengths. However, a revolution in mid-infrared light detection is underway based on the interactions of photons with superconducting materials, which function under fundamentally different operating principles. Superconducting detectors were first used to detect light at shorter wavelengths. However, recent developments in their sensitivity toward mid-infrared wavelengths up to 10 µm provide new opportunities for applications in molecular science, such as infrared emission experiments, exoplanet spectroscopy and single molecule microscopy. In this tutorial review, we provide background information needed for the non-expert in superconducting light detection to apply these devices in the field of mid-infrared molecular spectroscopy. We present and compare the detection mechanisms and current developments of three types of superconducting detectors: superconducting nanowire single-photon detectors (SNSPDs), transition edge sensors (TESs), and microwave kinetic inductance detectors (MKIDs). We also highlight existing applications of SNSPDs for laser-induced infrared fluorescence experiments and discuss their potential for other molecular spectroscopy applications. Ultimately, superconducting infrared detectors have the potential to approach the sensitivity and characteristics of established single-photon detectors operating in the UV/Vis region, which have existed for almost a century and become an indispensable tool within the field of physical chemistry.

Kilopixel array of superconducting nanowire single-photon detectors.

We present a 1024-element near-infrared imaging array of superconducting nanowire single photon detectors (SNSPDs) using a 32×32 row-column multiplexing architecture. The array has an active area of 0.96 × 0.96 mm, making it the largest SNSPD array reported to date in terms of both active area and pixel count. Using a 64-channel time-tagging readout, we have characterized the array's yield, efficiency, and timing resolution. Large arrays of SNSPDs are desirable for applications such as imaging, spectroscopy, or particle detection.

Mid-infrared Laser-Induced Fluorescence with Nanosecond Time Resolution Using a Superconducting Nanowire Single-Photon Detector: New Technology for Molecular Science.

In contrast to UV photomultiplier tubes that are widely used in physical chemistry, mid-infrared detectors are notorious for poor sensitivity and slow time response. This helps explain why, despite the importance of infrared spectroscopy in molecular science, mid-infrared fluorescence is not more widely used. In recent years, several new technologies have been developed that open new experimental possibilities for research in the mid-infrared. In this Account, we present one of the more promising technologies, superconducting nanowire single photon detectors (SNSPDs) by sharing our experience with its use in a typical experiment carried out by physical chemists (laser-induced fluorescence) and comparing the SNSPD to a detector commonly used by physical chemists (InSb at LN Temperature). SNSPDs are fabricated from a thin film of superconducting metal, patterned into a meandering nanowire. The nanowire is cooled below its superconducting temperature, Tc, and held in a constant current circuit below the critical current necessary to destroy superconductivity, Ic. Upon absorption of a photon, the resulting heat is sufficient to destroy superconductivity across the entire width of the nanowire, an event that can be detected as a voltage pulse. In contrast to semiconductor-based detectors, which have a long wavelength cutoff determined by the band gap, the SNSPD exhibits single-photon sensitivity across the entire mid-IR spectrum. As these devices have not been used extensively outside the field of light detection technology research, one important goal of this Account is to provide practical details for the implementation of these devices in a physical chemistry laboratory. We provide extensive Supporting Information describing what is needed. This includes information on a liquid nitrogen cooled monochromator, the optical collection system including mid-infrared fibers, as well as a closed-cycle cryogenic cooler that reaches 0.3 K. We demonstrate the advantages of these detectors in a time-resolved laser-induced infrared fluorescence experiment on the energy pooling in crystalline CO overlayers formed on a NaCl(100) surface. We present dispersed fluorescence spectra recorded from 1.9 to 7.0 µm obtained by single-photon counting. We also estimate the sensitivity of this WSi-based detection system at 3 µm; the system's noise equivalent power (NEP) value is ∼10-3 of a conventional InSb photovoltaic device. Straightforward modifications are expected to provide another 100 000-fold improvement. We demonstrate that the temporal resolution of the experiment is limited only by the pulse duration of the laser used in this work (fwhm = 3.7 ns). The use of SNSPDs enables dramatically improved observations of energy pooling in cryogenic molecular crystals.

Ultra-sensitive mid-infrared emission spectrometer with sub-ns temporal resolution.

We evaluate the performance of a mid-infrared emission spectrometer operating at wavelengths between 1.5 and 6 µm based on an amorphous tungsten silicide (a-WSi) superconducting nanowire single-photon detector (SNSPD). We performed laser induced fluorescence spectroscopy of surface adsorbates with sub-monolayer sensitivity and sub-nanosecond temporal resolution. We discuss possible future improvements of the SNSPD-based infrared emission spectrometer and its potential applications in molecular science.

Conclusive Experimental Demonstration of One-Way Einstein-Podolsky-Rosen Steering.

Einstein-Podolsky-Rosen steering is a quantum phenomenon wherein one party influences, or steers, the state of a distant party's particle beyond what could be achieved with a separable state, by making measurements on one-half of an entangled state. This type of quantum nonlocality stands out through its asymmetric setting and even allows for cases where one party can steer the other but where the reverse is not true. A series of experiments have demonstrated one-way steering in the past, but all were based on significant limiting assumptions. These consisted either of restrictions on the type of allowed measurements or of assumptions about the quantum state at hand, by mapping to a specific family of states and analyzing the ideal target state rather than the real experimental state. Here, we present the first experimental demonstration of one-way steering free of such assumptions. We achieve this using a new sufficient condition for nonsteerability and, although not required by our analysis, using a novel source of extremely high-quality photonic Werner states.

Efficient and pure femtosecond-pulse-length source of polarization-entangled photons.

We present a source of polarization entangled photon pairs based on spontaneous parametric downconversion engineered for frequency uncorrelated telecom photon generation. Our source provides photon pairs that display, simultaneously, the key properties for high-performance quantum information and fundamental quantum science tasks. Specifically, the source provides for high heralding efficiency, high quantum state purity and high entangled state fidelity at the same time. Among different tests we apply to our source we observe almost perfect non-classical interference between photons from independent sources with a visibility of (100 ± 5)%.

Heralded amplification of photonic qubits.

We demonstrate postselection free heralded qubit amplification for Time-Bin qubits and single photon states in an all-fibre, telecom-wavelength, scheme that highlights the simplicity, stability and potential for fully integrated photonic solutions. Exploiting high-efficiency superconducting detectors, the gain, fidelity and the performance of the amplifier are studied as a function of loss. We also demonstrate the first heralded single photon amplifier with independent sources. This provides a significant advance towards demonstrating device-independent quantum key distribution as well as fundamental tests of quantum mechanics over extended distances.

Spectral correlation and interference in non-degenerate photon pairs at telecom wavelengths.

We characterize an entangled-photon-pair source that produces signal and idler photons at 1533 nm and 1567 nm using fiber-assisted signal-photon spectroscopy. By erasing the polarization distinguishability, we observe interference between the two down-conversion paths. The observed interference signature is closely related to the spectral correlations between photons in a Hong-Ou-Mandel interferometer. These measurements suggest good indistinguishability between the two down-conversion paths, which is required for high entanglement visibility.

High-efficiency WSi superconducting nanowire single-photon detectors for quantum state engineering in the near infrared.

We report on high-efficiency superconducting nanowire single-photon detectors based on amorphous tungsten silicide and optimized at 1064 nm. At an operating temperature of 1.8 K, we demonstrated a 93% system detection efficiency at this wavelength with a dark noise of a few counts per second. Combined with cavity-enhanced spontaneous parametric downconversion, this fiber-coupled detector enabled us to generate narrowband single photons with a heralding efficiency greater than 90% and a high spectral brightness of 0.6×104 photons/(s·mW·MHz). Beyond single-photon generation at large rate, such high-efficiency detectors open the path to efficient multiple-photon heralding and complex quantum state engineering.

Temporal Multimode Storage of Entangled Photon Pairs.

Multiplexed quantum memories capable of storing and processing entangled photons are essential for the development of quantum networks. In this context, we demonstrate and certify the simultaneous storage and retrieval of two entangled photons inside a solid-state quantum memory and measure a temporal multimode capacity of ten modes. This is achieved by producing two polarization-entangled pairs from parametric down-conversion and mapping one photon of each pair onto a rare-earth-ion-doped (REID) crystal using the atomic frequency comb (AFC) protocol. We develop a concept of indirect entanglement witnesses, which can be used as Schmidt number witnesses, and we use it to experimentally certify the presence of more than one entangled pair retrieved from the quantum memory. Our work puts forward REID-AFC as a platform compatible with temporal multiplexing of several entangled photon pairs along with a new entanglement certification method, useful for the characterization of multiplexed quantum memories.

Strong Loophole-Free Test of Local Realism.

We present a loophole-free violation of local realism using entangled photon pairs. We ensure that all relevant events in our Bell test are spacelike separated by placing the parties far enough apart and by using fast random number generators and high-speed polarization measurements. A high-quality polarization-entangled source of photons, combined with high-efficiency, low-noise, single-photon detectors, allows us to make measurements without requiring any fair-sampling assumptions. Using a hypothesis test, we compute p values as small as 5.9×10^{-9} for our Bell violation while maintaining the spacelike separation of our events. We estimate the degree to which a local realistic system could predict our measurement choices. Accounting for this predictability, our smallest adjusted p value is 2.3×10^{-7}. We therefore reject the hypothesis that local realism governs our experiment.

A 64-pixel mid-infrared single-photon imager based on superconducting nanowire detectors.

A large-format mid-infrared single-photon imager with very low dark count rates would enable a broad range of applications in fields like astronomy and chemistry. Superconducting nanowire single-photon detectors (SNSPDs) are a mature photon-counting technology as demonstrated by their figures of merit such as high detection efficiencies and very low dark count rates. However, scaling SNSPDs to large array sizes for mid-infrared applications requires sophisticated readout architectures in addition to superconducting materials development. In this work, an SNSPD array design that combines a thermally coupled row-column multiplexing architecture with a thermally coupled time-of-flight transmission line was developed for mid-infrared applications. The design requires only six cables and can be scaled to larger array sizes. The demonstration of a 64-pixel array shows promising results for wavelengths between 3.4 µm and 10 µm, which will enable the use of this single-photon detector technology for a broad range of new applications.

Trap-Integrated Superconducting Nanowire Single-Photon Detectors with Improved RF Tolerance for Trapped-Ion Qubit State Readout.

State readout of trapped-ion qubits with trap-integrated detectors can address important challenges for scalable quantum computing, but the strong rf electric fields used for trapping can impact detector performance. Here, we report on NbTiN superconducting nanowire single-photon detectors (SNSPDs) employing grounded aluminum mirrors as electrical shielding that are integrated into linear surface-electrode rf ion traps. The shielded SNSPDs can be operated at applied rf trapping potentials of up to 54 Vpeak at 70 MHz and temperatures of up to 6 K, with a maximum system detection efficiency of 68 %. This performance should be sufficient to enable parallel high-fidelity state readout of a wide range of trapped ion species in typical cryogenic apparatus.

Quantum channel correction outperforming direct transmission.

Long-distance optical quantum channels are necessarily lossy, leading to errors in transmitted quantum information, entanglement degradation and, ultimately, poor protocol performance. Quantum states carrying information in the channel can be probabilistically amplified to compensate for loss, but are destroyed when amplification fails. Quantum correction of the channel itself is therefore required, but break-even performance-where arbitrary states can be better transmitted through a corrected channel than an uncorrected one-has so far remained out of reach. Here we perform distillation by heralded amplification to improve a noisy entanglement channel. We subsequently employ entanglement swapping to demonstrate that arbitrary quantum information transmission is unconditionally improved-i.e., without relying on postselection or post-processing of data-compared to the uncorrected channel. In this way, it represents realization of a genuine quantum relay. Our channel correction for single-mode quantum states will find use in quantum repeater, communication and metrology applications.

Demonstration of a polarization-entangled photon-pair source based on phase-modulated PPLN.

We develop and demonstrate a source of polarization-entangled photon pairs using spontaneous parametric down-conversion (SPDC) in domain-engineered, periodically poled lithium niobate (PPLN) at telecom wavelengths. Pumped at 775 nm, this domain-engineered type-II SPDC source produces non-degenerate signal and idler pairs at 1530 nm and 1569 nm. Because of birefringence, the photon pair with horizontally polarized signal and vertically polarized idler has a different phasematching condition than the pair with vertically polarized signal and horizontally polarized idler. Using phase-modulation of the domain structure, we produced a crystal that can simultaneously generate both states in a distributed fashion throughout a single crystal. Performing SPDC using this aperiodically poled crystal, we observed polarization entanglement visibility above 93%. We compare the phase-modulated crystal to other aperiodic structures, including dual-periodically-poled and interlaced biperiodic structures.

Connecting heterogeneous quantum networks by hybrid entanglement swapping.

Recent advances in quantum technologies are rapidly stimulating the building of quantum networks. With the parallel development of multiple physical platforms and different types of encodings, a challenge for present and future networks is to uphold a heterogeneous structure for full functionality and therefore support modular systems that are not necessarily compatible with one another. Central to this endeavor is the capability to distribute and interconnect optical entangled states relying on different discrete and continuous quantum variables. Here, we report an entanglement swapping protocol connecting such entangled states. We generate single-photon entanglement and hybrid entanglement between particle- and wave-like optical qubits and then demonstrate the heralded creation of hybrid entanglement at a distance by using a specific Bell-state measurement. This ability opens up the prospect of connecting heterogeneous nodes of a network, with the promise of increased integration and novel functionalities.

Observation of an isomerizing double-well quantum system in the condensed phase.

Molecular isomerization fundamentally involves quantum states bound within a potential energy function with multiple minima. For isolated gas-phase molecules, eigenstates well above the isomerization saddle points have been characterized. However, to observe the quantum nature of isomerization, systems in which transitions between the eigenstates occur-such as condensed-phase systems-must be studied. Efforts to resolve quantum states with spectroscopic tools are typically unsuccessful for such systems. An exception is CO adsorbed on NaCl(100), which is bound with the well-known OC-Na+ structure. We observe an unexpected upside-down isomer (CO-Na+) produced by infrared laser excitation and obtain well-resolved infrared fluorescence spectra from highly energetic vibrational states of both orientational isomers. This distinctive condensed-phase system is ideally suited to spectroscopic investigations of the quantum nature of isomerization.

The Sommerfeld ground-wave limit for a molecule adsorbed at a surface.

Using a mid-infrared emission spectrometer based on a superconducting nanowire single-photon detector, we observed the dynamics of vibrational energy pooling of carbon monoxide (CO) adsorbed at the surface of a sodium chloride (NaCl) crystal. After exciting a majority of the CO molecules to their first vibrationally excited state (v = 1), we observed infrared emission from states up to v = 27. Kinetic Monte Carlo simulations showed that vibrational energy collects in a few CO molecules at the expense of those up to eight lattice sites away by selective excitation of NaCl's transverse phonons. The vibrating CO molecules behave like classical oscillating dipoles, losing their energy to NaCl lattice vibrations via the electromagnetic near-field. This is analogous to Sommerfeld's description of radio transmission along Earth's surface by ground waves.

Heralded quantum steering over a high-loss channel.

Entanglement is the key resource for many long-range quantum information tasks, including secure communication and fundamental tests of quantum physics. These tasks require robust verification of shared entanglement, but performing it over long distances is presently technologically intractable because the loss through an optical fiber or free-space channel opens up a detection loophole. We design and experimentally demonstrate a scheme that verifies entanglement in the presence of at least 14.8 ± 0.1 dB of added loss, equivalent to approximately 80 km of telecommunication fiber. Our protocol relies on entanglement swapping to herald the presence of a photon after the lossy channel, enabling event-ready implementation of quantum steering. This result overcomes the key barrier in device-independent communication under realistic high-loss scenarios and in the realization of a quantum repeater.