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In an ultrafast nonlinear optical interaction, the electric field of the emitted nonlinear signal provides direct access to the induced nonlinear transient polarization or transient currents and thus carries signatures of ultrafast dynamics in a medium. Measurement of the electric field of such signals offers sensitive observables to track ultrafast electron dynamics in various systems. In this work, we resolve the real-time phase of the electric field of a femtosecond third-order nonlinear optical signal in the molecular frame. The electric field emitted from impulsively pre-aligned gas-phase molecules at room temperature, in a degenerate four-wave mixing scheme, is measured using a spectral interferometry technique. The nonlinear signal is measured around a rotational revival to extract its molecular-frame angle dependence from pump-probe time-delay scans. By comparing these measurements for two linear molecules, carbon dioxide and nitrogen, we show that the measured second-order phase parameter (temporal chirp) of the signal is sensitive to the valence electronic symmetry of the molecules, whereas the amplitude of the signal does not show such sensitivity. We compare measurements to theoretical calculations of the chirp observable in the molecular frame. This work is an important step towards using electric field measurements in nonlinear optical spectroscopy to study ultrafast dynamics of electronically excited molecules in the molecular frame. 

Large Language Models (LLMs) with strong abilities in natural language processing tasks have emerged and have been applied in various kinds of areas such as science, finance and software engineering. However, the capability of LLMs to advance the field of chemistry remains unclear. In this paper, rather than pursuing state-of-the-art performance, we aim to evaluate capabilities of LLMs in a wide range of tasks across the chemistry domain. We identify three key chemistryrelated capabilities including understanding, reasoning and explaining to explore in LLMs and establish a benchmark containing eight chemistry tasks. Our analysis draws on widely recognized datasets facilitating a broad exploration of the capacities of LLMs within the context of practical chemistry. Five LLMs (GPT-4, GPT-3.5, Davinci-003, Llama and Galactica) are evaluated for each chemistry task in zero-shot and few-shot in-context learning settings with carefully selected demonstration examples and specially crafted prompts. Our investigation found that GPT-4 outperformed other models and LLMs exhibit different competitive levels in eight chemistry tasks. In addition to the key findings from the comprehensive benchmark analysis, our work provides insights into the limitation of current LLMs and the impact of in-context learning settings on LLMs’ performance across various chemistry tasks. The code and datasets used in this study are available at https://github.com/ChemFoundationModels/ChemLLMBench. 

Dissolved organic nitrogen (DON) is the dominant form of bioavailable nitrogen in the euphotic zone of subtropical gyres, where nitrate (NO3-) concentrations are low. However, the spatial distribution of DON production and consumption in the surface ocean remains poorly resolved due to the relatively narrow range in euphotic zone DON concentrations. Recently, the stable isotopic composition (d15N) of DON has been used to identify DON production and consumption in the surface ocean, making isotopic measurements a more sensitive indicator of DON cycling than concentration measurements alone. Here we report DON concentration and d15N measurements in the upper ~300 m from a zonal transect along ~30˚S in the South Pacific (GO-SHIP P06-2017), including samples in the Western South Pacific (154˚E-170˚W), in the oligotrophic South Pacific Subtropical Gyre (110˚W -170˚W), and overlying the Oxygen Deficient Zone (ODZ) in the east (78˚W-110˚W). We observed small variations in surface DON concentrations. Surface DON in Western South Pacific, oligotrophic South Pacific Subtropical Gyre and above the ODZ are 4.6±1.0 µM, 4.3±0.7 µM, and 4.8±0.5 µM, respectively. d15N of DON in the euphotic zone is lower in the west and higher in the east, consistent with distributions of nitrogen fixation and denitrification, respectively, in the South Pacific. Similar decreasing trend in DON d15N in the euphotic zone and subsurface nitrate d15N was observed from the east to the west in the South Pacific, suggesting the d15N in subsurface nitrate could be imprinted in the DON d15N in the euphotic zone. Low surface ocean DON d15N in the Western South Pacific (2.4±1.8 ‰) and oligotrophic South Pacific Subtropical Gyre (2.6±1.6 ‰) compared with surface ocean DON d15N above ODZ (5.4±2.3 ‰) infer significant low-d15N nitrogen is added to the western South Pacific and oligotrophic South Pacific Subtropical Gyre, potentially from N2 fixation. Additionally, high DON d15N at ~180˚ was consistent with entrainment of subsurface NO3- into surface waters due to shallow bathymetry. Together, these observations suggest that DON production and consumption processes operate on timescales adequately fast to produce isotopic gradients across the South Pacific. Comparisons of surface ocean DON d15N with subsurface nitrate d15N constrain the locations and timescales of these processes. 

We report an experiment to measure the femtosecond electric field of the signal emitted from an optical third-order nonlinear interaction in carbon dioxide molecules. Using degenerate four-wave mixing with femtosecond near infrared laser pulses in combination with the ultra-weak femtosecond pulse measurement technique of TADPOLE, we measure the nonlinear signal electric field in the time domain at different time delays between the interacting pulses. The chirp extracted from the temporal phase of the emitted nonlinear signal is found to sensitively depend on the electronic and rotational contributions to the nonlinear response. While the rotational contribution results in a nonlinear signal chirp close to the chirp of the input pulses, the electronic contribution results in a significantly higher chirp which changes with time delay. Our work demonstrates that electric field-resolved nonlinear spectroscopy offers detailed information on nonlinear interactions at ultrafast time scales. 

1D organic metal halide hybrids (OMHHs) exhibit strongly anisotropic optical properties, highly efficient light emission, and large Stokes shift, holding promise for novel photodetection and lighting applications. However, the fundamental mechanisms governing their unique optical properties and in particular the impacts of surface effects are not understood. Herein, 1D C4N2H14PbBr4 by polarization-dependent time-averaged and time-resolved photoluminescence (TRPL) spectroscopy, as a function of photoexcitation energy, is investigated. Surprisingly, it is found that the emission under photoexcitation polarized parallel to the 1D metal halide chains can be either stronger or weaker than that under perpendicular polarization, depending on the excitation energy. The excitation-energy-dependent anisotropic emission is attributed to fast surface recombination, supported by first-principles calculations of optical absorption in this material. The fast surface recombination is directly confirmed by TRPL measurements, when the excitation is polarized parallel to the chains. The comprehensive studies provide a more complete picture for a deeper understanding of the optical anisotropy in 1D OMHHs.