Spin Unlocked Vortex Beam Generation on Nonlinear Chiroptical Metasurfaces.

Optical vortices with spin and orbital angular momentum (SAM and OAM) states offer multiple degrees of freedom for manipulating optical fields and thus enable great potentials in optical information processing. Recently, the optical metasurface has become an important platform for vortex beam generation and steering. However, the strong spin-orbit interaction on such metasurfaces usually leads to spin locked OAM generation, which limits the complete control of the angular momentum state of light. Here, we propose to solve this constraint using geometric phase controlled nonlinear chiroptical metasurfaces. The metasurface consists of two types of plasmonic meta-atoms which have opposite handedness and exhibit a strong spin-dependent circular dichroism effect. By encoding specific phase singularities and phase gradients to different channels, we experimentally demonstrate the spin unlocked second harmonic beam steering. The proposed nonlinear chiroptical metasurfaces may have important applications in developing multifunctional nonlinear optical devices.

All-optical ultrafast polarization switching with nonlinear plasmonic metasurfaces.

Optical switching has important applications in optical information processing, optical computing, and optical communications. The long-term pursuit of optical switch is to achieve short switching time and large modulation depth. Among various mechanisms, all-optical switching based on Kerr effect represents a promising solution. However, it is usually difficult to compromise both switching time and modulation depth of a Kerr-type optical switch. To circumvent this constraint, symmetry selective polarization switching via second-harmonic generation (SHG) in nonlinear crystals has been attracting scientists' attention. Here, we demonstrate SHG-based all-optical ultrafast polarization switching by using geometric phase controlled nonlinear plasmonic metasurfaces. A switching time of hundreds of femtoseconds and a modulation depth of 97% were experimentally demonstrated. The function of dual-channel all-optical switching was also demonstrated on a metasurface, which consists of spatially variant meta-atoms. The nonlinear metasurface proposed here represents an important platform for developing all-optical ultrafast switches and would benefit the area of optical information processing.

Solar cycle as a distinct line of evidence constraining Earth's transient climate response.

Severity of warming predicted by climate models depends on their Transient Climate Response (TCR). Inter-model spread of TCR has persisted at ~ 100% of its mean for decades. Existing observational constraints of TCR are based on observed historical warming response to historical forcing and their uncertainty spread is just as wide, mainly due to forcing uncertainty, and especially that of aerosols. Contrary, no aerosols are involved in solar-cycle forcing, providing an independent, tighter, constraint. Here, we define a climate sensitivity metric: time-dependent response regressed against time-dependent forcing, allowing phenomena with dissimilar time variations, such as the solar cycle with 11-year cyclic forcing, to be used to constrain TCR, which has a linear time-dependent forcing. We find a theoretical linear relationship between the two. The latest coupled atmosphere-ocean climate models obey the same linear relationship statistically. The proposed observational constraint on TCR is about [Formula: see text] as narrow as existing constraints. The central estimate, 2.2 oC, is at the midpoint of the spread of the latest generation of climate models, which are more sensitive than those of the previous generations.

A Centimeter-Scale Dielectric Metasurface for the Generation of Cold Atoms.

The single-beam magneto-optical trap (MOT) based on the diffractive optical element offers a new route to develop compact cold atom sources. However, the optical efficiency in the previous single-beam MOT systems is usually low and unbalanced, which will affect the quality of the trapped atoms. To solve this issue, we developed a centimeter-scale dielectric metasurface optical chip with dynamic phase distributions, which was used to split a single incident laser beam into five separate ones with well-defined polarization states and uniform energy distributions. The measured diffraction efficiency of the metasurface is up to 47%. A single-beam MOT integrated with the metasurface optical chip was then used to trap the 87Rb atoms with numbers ∼1.4 × 108 and temperatures ∼7.0 µK. The proposed concept in this work may provide a promising solution for developing ultracompact cold atom sources.

Seasonal Variations of Solar-Induced Fluorescence, Precipitation, and Carbon Dioxide Over the Amazon.

Previous studies suggested that the Amazon, the largest rainforest on Earth, changes from a CO2 sink to a CO2 source during the dry/fire season. However, the biospheric contributions to atmospheric CO2 are not well understood during the two main seasons, the dry/fire season and the wet season. In this article, we utilize Orbiting Carbon Observatory 2 (OCO-2) Solar-Induced Fluorescence (SIF) to explore photosynthetic activity during the different seasons. The spatiotemporal variability of OCO-2 SIF, OCO-2 CO2, precipitation, and burned area are investigated over the Amazon from September 2014 to December 2019. Averaging over the entire Amazon region, we found a positive temporal correlation (0.94) between OCO-2 SIF and Global Precipitation Climatology Project precipitation and a negative temporal correlation (-0.64) between OCO-2 SIF and OCO-2 CO2, consistent with the fact that precipitation enhances photosynthesis, which results in higher values for SIF and rate of removal of CO2 from the atmosphere above the Amazon region. We also observed seasonality in the spatial variability of these variables within the Amazon region. During the dry/fire (August-October) season, low SIF values, low precipitation, high vapor pressure deficit (VPD), large burned areas, and high atmospheric CO2 are mainly found over the southern Amazon region. In contrast, during the wet season (January-March), high SIF values, high precipitation, low VPD, smaller burned areas, and low CO2 are found over both the central and southern Amazon regions. The seasonal difference in SIF suggests that photosynthetic activity is reduced during the dry/fire season relative to the wet season as a result of low precipitation and high VPD, especially over the southern Amazon region, which will contribute to more CO2 in the atmosphere during the dry/fire season.

Nonlinear vectorial holography with quad-atom metasurfaces.

Vectorial optical holography represents a solution to control the polarization and amplitude distribution of light in the Fourier space. While vectorial optical holography has been experimentally demonstrated in the linear optical regime, its nonlinear counterpart, which can provide extra degrees of freedom of light-field manipulation through the frequency conversion processes, remains unexplored. Here, we experimentally demonstrate the nonlinear vectorial holography through the second harmonic generation process on a quad-atom plasmonic metasurface. The quad-atom metasurface consists of gold meta-atoms with threefold rotational symmetry. Based on the concept of nonlinear geometric phase, we can simultaneously manipulate the phase and amplitude of the left and right circularly polarized second harmonic waves generated from the quad-atom metasurface. By superposing the two orthogonal polarization components, the quad-atom metasurface can produce nonlinear holographic images with vectorial polarization distributions. The proposed metasurface platform may have important applications in vectorial polarization nonlinear optical source, high-capacity optical information storage, and optical encryption.

High-Order Nonlinear Spin-Orbit Interaction on Plasmonic Metasurfaces.

In linear optics, the angular momentum of light can be easily manipulated through the optical spin-orbit interaction (SOI) in structured media such as liquid crystals, metasurfaces, and forked gratings. Similarly, metasurfaces can be used to generate nonlinear optical beams with both custom-defined spin angular momentum (SAM) and orbital angular momentum (OAM) states. However, it has been limited to a low-order process in which only a Gaussian-shaped fundamental wave is used. In this work, the high-order nonlinear optical SOI effect on metasurfaces is demonstrated through the generation of multiple angular momentum states in nonlinear waves. This is achieved by exploiting the degrees of freedom provided by both the SAM and the OAM states of the fundamental wave (FW) and the topological charges of the plasmonic metasurfaces. The mechanism of both intrinsic and extrinsic contributions to the OAM of the nonlinear waves is revealed. High-order nonlinear SOI on metasurfaces offers new opportunities for realizing ultracompact nonlinear vortex beams.

Nonlinear Diatomic Metasurface for Real and Fourier Space Image Encoding.

In linear optics, the metasurface represents an ideal platform for encoding optical information because of its unprecedented abilities of manipulating the intensity, polarization, and phase of light wave with subwavelength meta-atoms. However, controlling various degrees of freedom of light in nonlinear optics remains elusive. Here, we propose a nonlinear plasmonic metasurface working in the near-infrared regime that can simultaneously encode optical images in the real and Fourier spaces. This is achieved by designing a diatomic meta-molecule, which enables the independent control of the nonlinear geometric phase, polarization, and intensity of second harmonic waves. The proposed nonlinear diatomic metasurface provides an ultracompact platform for implementing multidimensional optical information encoding and may hold great potential in optical information security and optical anticounterfeiting.

A dielectric metasurface optical chip for the generation of cold atoms.

Compact and robust cold atom sources are increasingly important for quantum research, especially for transferring cutting-edge quantum science into practical applications. In this study, we report on a novel scheme that uses a metasurface optical chip to replace the conventional bulky optical elements used to produce a cold atomic ensemble with a single incident laser beam, which is split by the metasurface into multiple beams of the desired polarization states. Atom numbers ~107 and temperatures (about 35 µK) of relevance to quantum sensing are achieved in a compact and robust fashion. Our work highlights the substantial progress toward fully integrated cold atom quantum devices by exploiting metasurface optical chips, which may have great potential in quantum sensing, quantum computing, and other areas.

Giant Enhancement of Second-Order Nonlinearity of Epsilon-near- Zero Medium by a Plasmonic Metasurface.

Nonlinear frequency conversion at the nanoscale is important for many applications in free space and integrated photonics. In epsilon-near-zero (ENZ) materials, second-harmonic generation (SHG) is significantly enhanced but the oblique incidence is required to address nonlinearity. To circumvent this constraint, we design a hybrid metasurface consisting of plasmonic nanostructures on an ENZ nanofilm generating strongly enhanced SHG at normal incidence in transmission. We show that the Au meta-atoms on an indium-tin-oxide (ITO) layer provide an approximately 104-fold experimentally measured SHG enhancement at normal incidence at the fundamental wavelength near the ENZ condition of ITO. This giant enhancement stems from reshaping the vectorial properties of the incident light near the Au nanostructures and its increased coupling to the ENZ film. The proposed hybrid ENZ metasurface offers a promising platform for developing ultracompact and efficient nonlinear optical sources at the nanoscale.

Interdecadal variability in pan-Pacific and global SST, revisited.

Interest in the "Interdecadal Pacific Oscillation (IPO)" in the global SST has surged recently on suggestions that the Pacific may be the source of prominent interdecadal variations observed in the global-mean surface temperature possibly through the mechanism of low-frequency modulation of the interannual El Nino-Southern Oscillation (ENSO) phenomenon. IPO was defined by performing empirical orthogonal function (EOF) analysis of low-pass filtered SST. The low-pass filtering creates its unique set of mathematical problems-in particular, mode mixing-and has led to some questions, many unanswered. To understand what these EOFs are, we express them first in terms of the recently developed pairwise rotated EOFs of the unfiltered SST, which can largely separate the high and low frequency bands without resorting to filtering. As reported elsewhere, the leading rotated dynamical modes (after the global warming trend) of the unfiltered global SST are: ENSO, Pacific Decadal Oscillation (PDO), and Atlantic Multidecadal Oscillation (AMO). IPO is not among them. The leading principal component (PC) of the low-pass filtered global SST is usually defined as IPO and it is seen to comprise of ENSO, PDO and AMO in various proportions depending on the filter threshold. With decadal filtering, the contribution of the interannual ENSO is understandably negligible. The leading dynamical mode of the filtered global SST is mostly AMO, and therefore should not have been called the Interdecadal "Pacific" Oscillation. The leading dynamical mode of the filtered pan-Pacific SST is mostly PDO. This and other low-frequency variability that have the action center in the Pacific, from either the pan-Pacific or global SST, have near zero global mean.

Diatomic Metasurface for Vectorial Holography.

The emerging metasurfaces with the exceptional capability of manipulating an arbitrary wavefront have revived the holography with unprecedented prospects. However, most of the reported metaholograms suffer from limited polarization controls for a restrained bandwidth in addition to their complicated meta-atom designs with spatially variant dimensions. Here, we demonstrate a new concept of vectorial holography based on diatomic metasurfaces consisting of metamolecules formed by two orthogonal meta-atoms. On the basis of a simply linear relationship between phase and polarization modulations with displacements and orientations of identical meta-atoms, active diffraction of multiple polarization states and reconstruction of holographic images are simultaneously achieved, which is robust against both incident angles and wavelengths. Leveraging this appealing feature, broadband vectorial holographic images with spatially varying polarization states and dual-way polarization switching functionalities have been demonstrated, suggesting a new route to achromatic diffractive elements, polarization optics, and ultrasecure anticounterfeiting.

Midlatitude atmospheric OH response to the most recent 11-y solar cycle.

The hydroxyl radical (OH) plays an important role in middle atmospheric photochemistry, particularly in ozone (O(3)) chemistry. Because it is mainly produced through photolysis and has a short chemical lifetime, OH is expected to show rapid responses to solar forcing [e.g., the 11-y solar cycle (SC)], resulting in variabilities in related middle atmospheric O(3) chemistry. Here, we present an effort to investigate such OH variability using long-term observations (from space and the surface) and model simulations. Ground-based measurements and data from the Microwave Limb Sounder on the National Aeronautics and Space Administration's Aura satellite suggest an ∼7-10% decrease in OH column abundance from solar maximum to solar minimum that is highly correlated with changes in total solar irradiance, solar Mg-II index, and Lyman-α index during SC 23. However, model simulations using a commonly accepted solar UV variability parameterization give much smaller OH variability (∼3%). Although this discrepancy could result partially from the limitations in our current understanding of middle atmospheric chemistry, recently published solar spectral irradiance data from the Solar Radiation and Climate Experiment suggest a solar UV variability that is much larger than previously believed. With a solar forcing derived from the Solar Radiation and Climate Experiment data, modeled OH variability (∼6-7%) agrees much better with observations. Model simulations reveal the detailed chemical mechanisms, suggesting that such OH variability and the corresponding catalytic chemistry may dominate the O(3) SC signal in the upper stratosphere. Continuing measurements through SC 24 are required to understand this OH variability and its impacts on O(3) further.

Design, synthesis, characterization, luminescence and non-linear optical (NLO) properties of multinuclear platinum(II) alkynyl complexes.

A series of luminescent multinuclear platinum(II) alkynyl complexes containing triethynylbenzene or 1,4-bis(3,5-diethynylphenyl)buta-1,3-diyne as cores has been successfully synthesized and characterized. The electronic absorption, emission, nanosecond transient absorption and electrochemical properties of these complexes have been reported. These complexes show long-lived emissions in degassed benzene solution and in alcoholic glass at 77 K. Moreover, they are found to exhibit two-photon absorption (2PA) and two-photon induced luminescence (TPIL) properties, and their two-photon absorption cross-sections have been determined to be 6-191 GM upon excitation at 720 nm. Through a systematic comparison, it has been found that tetra- and hexanuclear platinum(II) complexes show better 2PA and TPIL properties than their di- and trinuclear counterparts.

Tropical mid-tropospheric CO2 variability driven by the Madden-Julian oscillation.

Carbon dioxide (CO(2)) is the most important anthropogenic greenhouse gas in the present-day climate. Most of the community focuses on its long-term (decadal to centennial) behaviors that are relevant to climate change, but there are relatively few discussions of its higher-frequency forms of variability, and none regarding its subseasonal distribution. In this work, we report a large-scale intraseasonal variation in the Atmospheric Infrared Sounder CO(2) data in the global tropical region associated with the Madden-Julian oscillation (MJO). The peak-to-peak amplitude of the composite MJO modulation is ∼1 ppmv, with a standard error of the composite mean < 0.1 ppmv. The correlation structure between CO(2) and rainfall and vertical velocity indicate positive (negative) anomalies in CO(2) arise due to upward (downward) large-scale vertical motions in the lower troposphere associated with the MJO. These findings can help elucidate how faster processes can organize, transport, and mix CO(2) and provide a robustness test for coupled carbon-climate models.

Atmospheric pressure as a natural climate regulator for a terrestrial planet with a biosphere.

Lovelock and Whitfield suggested in 1982 that, as the luminosity of the Sun increases over its life cycle, biologically enhanced silicate weathering is able to reduce the concentration of atmospheric carbon dioxide (CO(2)) so that the Earth's surface temperature is maintained within an inhabitable range. As this process continues, however, between 100 and 900 million years (Ma) from now the CO(2) concentration will reach levels too low for C(3) and C(4) photosynthesis, signaling the end of the solar-powered biosphere. Here, we show that atmospheric pressure is another factor that adjusts the global temperature by broadening infrared absorption lines of greenhouse gases. A simple model including the reduction of atmospheric pressure suggests that the life span of the biosphere can be extended at least 2.3 Ga into the future, more than doubling previous estimates. This has important implications for seeking extraterrestrial life in the Universe. Space observations in the infrared region could test the hypothesis that atmospheric pressure regulates the surface temperature on extrasolar planets.

Reactivity of aqua coordinated monoporphyrinate lanthanide complexes: synthetic, structural and photoluminescent studies of lanthanide porphyrinate dimers.

Dimerization of monoporphyrinate lanthanide complexes [Yb(Por)(H(2)O)(3)]Cl, (Por = TTP(2-), TMPP(2-) and TPP(2-)) in the presence of sterically hindered tripodal ligand, zinc Schiff-base, dilute HCl, K(2)CO(3) solution, 4,4'-bipyridine (bipy), and basic 8-hydroxyquinaldine (HQ) solution was observed in CH(2)Cl(2) at room temperature. Six neutral dimeric lanthanide porphyrinate complexes, [Yb(TTP)(mu-OH)](2)(mu-THF) (1), [Yb(TMPP)(mu-OH)(H(2)O)](2) (2), [Yb(TPP)(mu-OH)(mu-H(2)O)](2) (4), [Yb(TMPP)(mu-Cl)(H(2)O)](2) (5), [Yb(TMPP)(mu-OH)](2)(THF) (6) and [Yb(TPP)](2)(mu-OH)(mu-Q) (7), were obtained. X-Ray diffraction studies showed that for the dimers, the two lanthanide ions were bridged by OH(-), Cl(-) or H(2)O. Photoluminescent studies showed that the porphyrinate dianion acted as an antenna, transferred its absorbed visible energy to the lanthanide ion and enabled the latter emitting in the near-infrared (NIR) region. In general, the NIR emission is more intense for the dimers than for the monomers, and the NIR emission intensity decreases as the number of O-H oscillators present in the molecule increases.

Syntheses, crystal structures, and physical properties of dinuclear copper(I) and tetranuclear mixed-valence copper(I,II) complexes with hydroxylated bipyridyl-like ligands.

Four copper complexes with hydroxylated bipyridyl-like ligands, namely [Cu(2)(ophen)(2)] (1), [Cu(4)(ophen)(4)(tp)] (2), [Cu(4)(obpy)(4)(tp)] (3), and [Cu(4)(obpy)(4)(dpdc)].2H(2)O (4), (Hophen=2-hydroxy-1,10-phenanthroline, Hobpy=6-hydroxy-2,2'-bipyridine, tp=terephthalate, dpdc=diphenyl-4,4'-dicarboxylate) have been synthesized hydrothermally. X-ray single-crystal structural analyses of these complexes reveal that 1,10-phenanthroline (phen) or 2,2'-bipyridine (bpy) ligands are hydroxylated into ophen or obpy during the reaction, which provides structural evidence for the long-time argued Gillard mechanism. The dinuclear copper(I) complex 1 has three supramolecular isomers in the solid state, in which short copper-copper distances (2.66-2.68 A) indicate weak metal-metal bonding interactions. Each of the mixed-valence copper(i,ii) complexes 2-4 consists of a pair of [Cu(2)(ophen)(2)](+) or [Cu(2)(obpy)(2)](+) fragments bridged by a dicarboxylate ligand into a neutral tetranuclear dumbbell structure. Dinuclear 1 is an intermediate in the formation of 2 and can be converted into 2 in the presence of additional copper(II) salt and tp ligands under hydrothermal conditions. In addition to the ophen-centered pi-->pi* excited-state emission, 1 shows strong emissions at ambient temperature, which may be tentatively assigned as an admixture of copper-centered d-->s,p and MLCT excited states.

[Lanthanide ion luminescence probe: low temperature phase transition of EuS4N complex].

Fluorescence spectrum of EuS4N complex at low temperature is very different from that at room temperature. When temperature changes, shapes of both excitation and emission spectra change dramatically at about 160 K, which is taken as an indicator of the structural change of EuS4N. Peak splitting of 5D0-->7F0 also indicates that there are two different types of coordination structure for Eu3+ ions at low temperature, while only one at room temperature. Thermal effect for the structure transition is also deduced from the relation between fluorescence intensity and temperature changing manner. These results were in good accordance with directly measurement on sample temperature. The reason for the structure change is also discussed from the structure of the EuS4N complex. This study proved that lanthanide luminescent probe, as a complementarity to X-ray diffraction technique, should be an effective tool in low temperature crystal structure study.