Photostriction in Ferroelectrics from Density Functional Theory

International audienceAn ab initio procedure allowing the computation of the deformation of ferroelectric-based materials under light is presented. This numerical scheme consists in structurally relaxing the system under the constraint of a fixed n e concentration of electrons photoexcited into a specific conduction band edge state from a chosen valence band state, via the use of a constrained density functional theory method. The resulting change in lattice constant along a selected crystallographic direction is then calculated for a reasonable estimate of n e. This method is applied to bulk multiferroic BiFeO 3 and predicts a photostriction effect of the same order of magnitude than the ones recently observed. A strong dependence of photostrictive response on both the reached conduction state and the crystallographic direction (along which this effect is determined) is also revealed. Furthermore, analysis of the results demonstrates that the photostriction mechanism mostly originates from the screening of the spontaneous polarization by the photoexcited electrons in combination with the inverse piezoelectric effect. The coupling of ferroelectric or multiferroic materials with light is currently attracting a lot of attention [1], as, e.g., demonstrated by the above-band-gap photovoltages found in BiFeO 3 (BFO) thin films [2], the search of low band gap materials for photovoltaic applications [3], or the recent development in the so-called hybrid perovskite solar cells [4]. Beyond the photovoltaic effect, there is another coupling between light and properties of ferroelectrics or multiferroics that is of current interest, namely, the so-called photostriction effect, a deformation of the material under illumination [5]. The photostriction phenomenon opens new perspectives for combining several functionalities in future generations of remote switchable devices and is promising for the realization of light-induced actuators [5]. It has been recently observed in BFO under visible light [6,7]. A giant shear strain generated by femtosecond laser pulses was also reported [8,9], and time-resolved synchrotron diffraction reported a shift of the Bragg peak on a picosecond time scale in both bismuth ferrite [10] and lead titanate [11]. However, the microscopic mechanism responsible for photostriction is poorly understood [8,9]. Obviously, having accurate numerical techniques able to tackle photostriction will allow us to " shed some light " on this effect. However, to the best of our knowledge, such numerical tools allowing a systematic study of the photostriction phenomenon and its atomistic origin are not available yet, despite recent attempts to use Density Functional Theory (DFT) as a tool to fit x-ray absorption spectra in pump-probe photostriction experiments [12]. Here, we report the development of an ab initio procedure to compute photostriction from first principles. This procedure not only reproduces the order of magnitude of the observed change of lattice constant in BFO [6], but also reveals that photostriction mostly originates from the combination of the screening of the polarization by the electrons photoejected in the conduction band and the inverse piezoelectric effect. It is also found that photo-striction depends on the precise conduction state the electron is excited into, and on the crystallographic direction along which the effect is studied. In order to realize the difficulty in mimicking photo-striction, let us start by recalling that the Kohn-Sham (KS) implementation of DFT [13] reformulates the many-body problem of interacting electrons into many single-body problems, and " only " guarantees that the model noninter-acting KS Hamiltonian yields the same ground state density and energy as the real interacting Hamiltonian. Such a fact, therefore, leaves the description of unoccupied states within traditional DFT an unanswered question, and the determination of excitation energies remains the privilege of rather costly techniques, such as time-dependent DFT [14] or the GW approximation [15]. However, an alternative formulation of DFT that treats ground and excited states on the same footing has been proposed [16]. In particular, Ref. [16] connected each eigenstate of a real interacting Hamiltonian with the eigenstate of a model noninteracting Hamiltonian through a generalized adiabatic connection (GAC) scheme. The so-called ΔSCF method [17] takes advantage of this GAC scheme, and assumes an one-to-one correspondence between the excited states of a single Kohn-Sham system and the real system [16]. This ΔSCF scheme has proved successful and computationall

Simulated last glacial maximum D14Catm and the deep glacial ocean carbon reservoir

∆14Catm has been estimated as 420 ± 80‰ (IntCal09) during the Last Glacial Maximum (LGM) compared to preindustrial times (0‰), but mechanisms explaining this difference are not yet resolved. ∆14Catm is a function of both cosmogenic production in the high atmosphere and of carbon cycling and partitioning in the Earth system. 10Be-based reconstructions show a contribution of the cosmogenic production term of only 200 ± 200‰ in the LGM. The remaining 220‰ have thus to be explained by changes in the carbon cycle. Recently, Bouttes et al. (2010, 2011) proposed to explain most of the difference in pCO2atm and δ13C between glacial and interglacial times as a result of brine-induced ocean stratification in the Southern Ocean. This mechanism involves the formation of very saline water masses that contribute to high carbon storage in the deep ocean. During glacial times, the sinking of brines is enhanced and more carbon is stored in the deep ocean, lowering pCO2atm. Moreover, the sinking of brines induces increased stratification in the Southern Ocean, which keeps the deep ocean well isolated from the surface. Such an isolated ocean reservoir would be characterized by a low ∆14C signature. Evidence of such 14C-depleted deep waters during the LGM has recently been found in the Southern Ocean (Skinner et al. 2010). The degassing of this carbon with low ∆14C would then reduce ∆14Catm throughout the deglaciation. We have further developed the CLIMBER-2 model to include a cosmogenic production of 14C as well as an interactive atmospheric 14C reservoir. We investigate the role of both the sinking of brine and cosmogenic production, alongside iron fertilization mechanisms, to explain changes in ∆14Catm during the last deglaciation. In our simulations, not only is the sinking of brine mechanism consistent with past ∆14C data, but it also explains most of the differences in pCO2atm and ∆14Catm between the LGM and preindustrial times. Finally, this study represents the first time to our knowledge that a model experiment explains glacial-interglacial differences in pCO2atm, δ13C, and ∆14C together with a coherent LGM climate

Lithium bis­(2-methyl­lactato)borate monohydrate

The title compound {systematic name: poly[[aqua­lithium]-μ-3,3,8,8-tetra­methyl-1,4,6,9-tetra­oxa-5λ4-borataspiro­[4.4]nonane-2,7-dione]}, [Li(C8H12BO6)(H2O)]n (LiBMLB), forms a 12-membered macrocycle, which lies across a crystallographic inversion center. The lithium cations are pseudo-tetra­hedrally coordinated by three methyl­lactate ligands and a water mol­ecule. The asymmetric units couple across crystallographic inversion centers, forming the 12-membered macrocycles. These macrocycles, in turn, cross-link through the Li+ cations, forming an infinite polymeric structure in two dimensions parallel to (101)

Impact of oceanic processes on the carbon cycle during the last termination

During the last termination (from ~18 000 years ago to ~9000 years ago), the climate significantly warmed and the ice sheets melted. Simultaneously, atmospheric CO2 increased from ~190 ppm to ~260 ppm. Although this CO2 rise plays an important role in the deglacial warming, the reasons for its evolution are difficult to explain. Only box models have been used to run transient simulations of this carbon cycle transition, but by forcing the model with data constrained scenarios of the evolution of temperature, sea level, sea ice, NADW formation, Southern Ocean vertical mixing and biological carbon pump. More complex models (including GCMs) have investigated some of these mechanisms but they have only been used to try and explain LGM versus present day steady-state climates. In this study we use a coupled climate-carbon model of intermediate complexity to explore the role of three oceanic processes in transient simulations: the sinking of brines, stratification-dependent diffusion and iron fertilization. Carbonate compensation is accounted for in these simulations. We show that neither iron fertilization nor the sinking of brines alone can account for the evolution of CO2, and that only the combination of the sinking of brines and interactive diffusion can simultaneously simulate the increase in deep Southern Ocean δ13C. The scenario that agrees best with the data takes into account all mechanisms and favours a rapid cessation of the sinking of brines around 18 000 years ago, when the Antarctic ice sheet extent was at its maximum. In this scenario, we make the hypothesis that sea ice formation was then shifted to the open ocean where the salty water is quickly mixed with fresher water, which prevents deep sinking of salty water and therefore breaks down the deep stratification and releases carbon from the abyss. Based on this scenario, it is possible to simulate both the amplitude and timing of the long-term CO2 increase during the last termination in agreement with ice core data. The atmospheric δ13C appears to be highly sensitive to changes in the terrestrial biosphere, underlining the need to better constrain the vegetation evolution during the termination

Carbon superatom thin films

Assembling clusters on surfaces has emerged as a novel way to grow thin films with targeted properties. In particular, it has been proposed from experimental findings that fullerenes deposited on surfaces could give rise to thin films retaining the bonding properties of the incident clusters. However the microscopic structure of such films is still unclear. By performing quantum molecular dynamics simulations, we show that C_28 fullerenes can be deposited on a surface to form a thin film of nearly defect free molecules, which act as carbon superatoms. Our findings help clarify the structure of disordered small fullerene films and also support the recently proposed hyperdiamond model for solid C_28.Comment: 13 pages, RevTeX, 2 figures available as black and white PostScript files; color PostScript and/or gif files available upon reques

Non-equilibrium transport through a vertical quantum dot in the absence of spin-flip energy relaxation

We investigate non-equilibrium transport in the absence of spin-flip energy relaxation in a few-electron quantum dot artificial atom. Novel non-equilibrium tunneling processes involving high-spin states which cannot be excited from the ground state because of spin-blockade, and other processes involving more than two charge states are observed. These processes cannot be explained by orthodox Coulomb blockade theory. The absence of effective spin relaxation induces considerable fluctuation of the spin, charge, and total energy of the quantum dot. Although these features are revealed clearly by pulse excitation measurements, they are also observed in conventional dc current characteristics of quantum dots.Comment: accepted for publication in Phys. Rev.Let

Variations in Longitudinal Permeability of Coastal Western Hemlock

The air permeability of western hemlock from coastal forests in western Oregon was assessed. Permeability varied widely among trees, as well as by position within individual trees. Permeability tended to decrease with distance inward from the bark, a trend implying that this species produces a heartwood zone. These variations may help to explain the treatability differences observed in lumber of this species

Quantifying the roles of ocean circulation and biogeochemistry in governing ocean carbon-13 and atmospheric carbon dioxide at the last glacial maximum

We use a state-of-the-art ocean general circulation and biogeochemistry model to examine the impact of changes in ocean circulation and biogeochemistry in governing the change in ocean carbon-13 and atmospheric CO2 at the last glacial maximum (LGM). We examine 5 different realisations of the ocean's overturning circulation produced by a fully coupled atmosphere-ocean model under LGM forcing and suggested changes in the atmospheric deposition of iron and phytoplankton physiology at the LGM. Measured changes in carbon-13 and carbon-14, as well as a qualitative reconstruction of the change in ocean carbon export are used to evaluate the results. Overall, we find that while a reduction in ocean ventilation at the LGM is necessary to reproduce carbon-13 and carbon-14 observations, this circulation results in a low net sink for atmospheric CO2. In contrast, while biogeochemical processes contribute little to carbon isotopes, we propose that most of the change in atmospheric CO2 was due to such factors. However, the lesser role for circulation means that when all plausible factors are accounted for, most of the necessary CO2 change remains to be explained. This presents a serious challenge to our understanding of the mechanisms behind changes in the global carbon cycle during the geologic past