Calibration of a CubeSat spectroradiometer with a narrow-band widely tunable radiance source.

We have developed an SI-traceable narrow-band tunable radiance source based on an optical parametric oscillator (OPO) and an integrating sphere for the calibration of spectroradiometers. The source is calibrated with a reference detector over the ultraviolet/visible spectral range with an uncertainty of <1%. As a case study, a CubeSat spectroradiometer has been calibrated for radiance over its operating range from 370 nm to 480 nm. To validate the results, the instrument has also been calibrated with a traditional setup based on a diffuser and an FEL lamp. Both routes show good agreement within the combined measurement uncertainty. The OPO-based approach could be an interesting alternative to the traditional method, not only because of reduced measurement uncertainty, but also because it directly allows for wavelength calibration and characterization of the instrumental spectral response function and stray light effects, which could reduce calibration time and cost.

Entanglement between a Diamond Spin Qubit and a Photonic Time-Bin Qubit at Telecom Wavelength.

We report on the realization and verification of quantum entanglement between a nitrogen-vacancy electron spin qubit and a telecom-band photonic qubit. First we generate entanglement between the spin qubit and a 637 nm photonic time-bin qubit, followed by photonic quantum frequency conversion that transfers the entanglement to a 1588 nm photon. We characterize the resulting state by correlation measurements in different bases and find a lower bound to the Bell state fidelity of ≥0.77±0.03. This result presents an important step towards extending quantum networks via optical fiber infrastructure.

Femtosecond time-resolved and two-dimensional vibrational sum frequency spectroscopic instrumentation to study structural dynamics at interfaces.

We present a novel setup to elucidate the dynamics of interfacial molecules specifically, using surface-selective femtosecond vibrational spectroscopy. The approach relies on a fourth-order nonlinear optical interaction at the interface. In the experiments, interfacial molecules are vibrationally excited by an intense, tunable femtosecond midinfrared (2500-3800 cm(-1)) pump pulse, resonant with the molecular vibrations. The effect of the excitation and the subsequent relaxation to the equilibrium state are probed using broadband infrared+visible sum frequency generation (SFG) light, which provides the transient vibrational spectrum of interfacial molecules specifically. This IR pump-SFG probe setup has the ability to measure both vibrational population lifetimes as well as the vibrational coupling between different chemical moieties at interfaces. Vibrational lifetimes of interfacial molecules are determined in one-dimensional pump-SFG probe experiments, in which the response is monitored as a function of the delay between the pump and probe pulses. Vibrational coupling between molecular groups is determined in two-dimensional pump-SFG probe experiments, which monitor the response as a function of pump and probe frequencies at a fixed delay time. To allow for one setup to perform these multifaceted experiments, we have implemented several instrumentation techniques described here. The detection of the spectrally resolved differential SFG signal using a combination of a charge-coupled device camera and a piezocontrolled optical scanner, computer-controlled Fabry-Perot etalons to shape and scan the IR pump pulse and the automated sample dispenser and sample trough height corrector are some of the novelties in this setup.

Controlling the efficiency of an artificial light-harvesting complex.

Adaptive femtosecond pulse shaping in an evolutionary learning loop is applied to a bioinspired dyad molecule that closely mimics the early-time photophysics of the light-harvesting complex 2 (LH2) photosynthetic antenna complex. Control over the branching ratio between the two competing pathways for energy flow, internal conversion (IC) and energy transfer (ET), is realized. We show that by pulse shaping it is possible to increase independently the relative yield of both channels, ET and IC. The optimization results are analyzed by using Fourier analysis, which gives direct insight to the mechanism featuring quantum interference of a low-frequency mode. The results from the closed-loop experiments are repeatable and robust and demonstrate the power of coherent control experiments as a spectroscopic tool (i.e., quantum-control spectroscopy) capable of revealing functionally relevant molecular properties that are hidden from conventional techniques.

Ultrafast energy transfer dynamics of a bioinspired dyad molecule.

A caroteno-purpurin dyad molecule was studied by steady-state and pump-probe spectroscopies to resolve the excited-state deactivation dynamics of the different energy levels as well as the connecting energy flow pathways and corresponding rate constants. The data were analyzed with a two-step multi-parameter global fitting procedure that makes use of an evolutionary algorithm. We found that following ultrafast excitation of the donor (carotenoid) chromophore to its S2 state, the energy flows via two channels: energy transfer (70%) and internal conversion (30%) with time constants of 54 and 110 fs, respectively. Additionally, some of the initial excitation is found to populate the hot ground state, revealing another limitation to the functional efficiency. At later times, a back transfer occurs from the purpurin to the carotenoid triplet state in nanosecond timescales. Details of the energy flow within the dyad as well as species associated spectra are disentangled for all excited-state and ground-state species for the first time. We also observe oscillations with the most pronounced peak on the Fourier transform spectrum having a frequency of 530 cm(-1). The dyad mimics the dynamics of the natural light-harvesting complex LH2 from Rhodopseudomonas acidophila and is hence a good model system to be used in studies aimed to further explain previous work in which the branching ratio between the competing pathways of energy loss and energy transfer could be manipulated by adaptive femtosecond pulse shaping.