No Arabic abstract
The torsional Raman spectra of two astrophysically detected isotopologues of dimethyl-ether, ($^{12}$CH$_3$O$^{12}$CH$_3$ and $^{13}$CH$_3$O$^{12}$CH$_3$), have been recorded at room temperature and cooled in supersonic jet, and interpreted with the help of highly correlated ab initio calculations. Dimethyl-ether displays excited torsional and vibrational levels at low energy that can be populated at the temperatures of the star forming regions, obliging to extend the analysis of the rotational spectrum over the ground state. Its spectrum in the THz region is rather complex due to the coupling of the torsional overtones $2 u_{11}$ and $2 u_{15}$ with the COC bending mode, and the presence of many hot bands. The torsional overtones are set here at $2 u_{11}=385.2$~cm$^{-1}$ and $2 u_{15}=482.0$~cm$^{-1}$ for $^{12}$CH$_3$O$^{12}$CH$_3$, and $2 u_{11}=385.0$~cm$^{-1}$ and $2 u_{15}=481.1$~cm$^{-1}$ for $^{13}$CH$_3$O$^{12}$CH$_3$. The new assignment of $2 u_{11}$ is downshifted around $sim 10$~cm$^{-1}$ with respect to the literature. All the other (hot) bands have been re-assigned consistently. In addition, the infrared-forbidden torsional fundamental band $ u_{11}$ is observed here at 197.8~cm$^{-1}$. The new spectral characterization in the THz region reported here provides improved values of the Hamiltonian parameters, to be used in the analysis of the rotational spectra of DME isotopologues for further astrophysical detections.
Hybrid halide perovskites exhibit nearly 20% power conversion efficiency, but the origin of their high efficiency is still unknown. Here, we compute the shift current, a dominant mechanism of bulk photovoltaic (PV) effect for ferroelectric photovoltaics, in CH$_3$NH$_3$PbI$_3$ and CH$_3$NH$_3$PbI$_{3-x}$Cl$_{x}$ from first principles. We find that these materials give approximately three times larger shift current PV response to near-IR and visible light than the prototypical ferroelectric photovoltaic BiFeO$_3$. The molecular orientations of CH$_3$NH$_3^{+}$ can strongly affect the corresponding PbI$_3$ inorganic frame so as to alter the magnitude of the shift current response. Specifically, configurations with dipole moments aligned in parallel distort the inorganic PbI$_3$ frame more significantly than configurations with near net zero dipole, yielding a larger shift current response. Furthermore, we explore the effect of Cl substitution on shift current, and find that Cl substitution at the equatorial site induces a larger response than does substitution at the apical site.
Titan harbors a dense, organic-rich atmosphere primarily composed of N$_2$ and CH$_4$, with lesser amounts of hydrocarbons and nitrogen-bearing species. As a result of high sensitivity observations by the Atacama Large Millimeter/submillimeter Array (ALMA) in Band 6 ($sim$230-272 GHz), we obtained the first spectroscopic detection of CH$_3$C$_3$N (methylcyanoacetylene or cyanopropyne) in Titans atmosphere through the observation of seven transitions in the $J = 64rightarrow63$ and $J = 62rightarrow61$ rotational bands. The presence of CH$_3$C$_3$N on Titan was suggested by the Cassini Ion and Neutral Mass Spectrometer detection of its protonated form: C$_4$H$_3$NH$^+$, but the atmospheric abundance of the associated (deprotonated) neutral product is not well constrained due to the lack of appropriate laboratory reaction data. Here, we derive the column density of CH$_3$C$_3$N to be (3.8-5.7)$times10^{12}$ cm$^{-2}$ based on radiative transfer models sensitive to altitudes above 400 km Titans middle atmosphere. When compared with laboratory and photochemical model results, the detection of methylcyanoacetylene provides important constraints for the determination of the associated production pathways (such as those involving CN, CCN, and hydrocarbons), and reaction rate coefficients. These results also further demonstrate the importance of ALMA and (sub)millimeter spectroscopy for future investigations of Titans organic inventory and atmospheric chemistry, as CH$_3$C$_3$N marks the heaviest polar molecule detected spectroscopically in Titans atmosphere to date.
Instability of perovskite photovoltaics is still a topic which is currently under intense debate, especially the role of water environment. Unraveling the mechanism of this instability is urgent to enable practical application of perovskite solar cells. Here, ab initio metadynamics is employed to investigate the initial phase of a dissolution process of CH$_3$NH$_3$PbI$_3$ (MAPbI$_3$) in explicit water. It is found that the initial dissolution of MAPbI$_3$ is a complex multi-step process triggered by the departure of I$^-$ ion from the CH$_3$NH$_3$I-terminated surface. Reconstruction of the free energy landscape indicates a low energy barrier for water dissolution of MAPbI$_3$. In addition, we propose a two-step thermodynamic cycle for MAPbI$_3$ dissolution in water at a finite concentration that renders a spontaneity of the dissolution process. The low energy barrier for the initial dissolution step and the spontaneous nature of MAPbI$_3$ dissolution in water explain why the water immediately destroys pristine MAPbI$_3$. The dissolution thermodynamics of all-inorganic CsPbI$_3$ perovskite is also analyzed for comparison. Hydration enthalpies and entropies of aqueous ions play an important role for the dissolution process. Our findings provide a comprehensive understanding to the current debate on water instability of MAPbI$_3$.
The organic-inorganic lead halide perovskites are composed of organic molecules imbedded in an inorganic framework. The compounds with general formula CH$_{3}$NH$_{3}$PbX$_{3}$ (MAPbX$_{2}$) display large photovoltaic efficiencies for halogens $X$=Cl, Br, and I in a wide variety of sample geometries and preparation methods. The organic cation and inorganic framework are bound by hydrogen bonds that tether the molecules to the halide anions, and this has been suggested to be important to the optoelectronic properties. We have studied the effects of this bonding using time-of-flight neutron spectroscopy to measure the molecular dynamics in CH$_3$NH$_3$PbCl$_3$ (MAPbCl$_3$). Low-energy/high-resolution neutron backscattering reveals thermally-activated molecular dynamics with a characteristic temperature of $sim$ 95,K. At this same temperature, higher-energy neutron spectroscopy indicates the presence of an anomalous broadening in energy (reduced lifetime) associated with the molecular vibrations. By contrast, neutron powder diffraction shows that a spatially long-range structural phase transitions occurs at 178,K (cubic $rightarrow$ tetragonal) and 173,K (tetragonal $rightarrow$ orthorhombic). The large difference between these two temperature scales suggests that the molecular and inorganic lattice dynamics in MAPbCl$_3$ are actually decoupled. With the assumption that underlying physical mechanisms do not change with differing halogens in the organic-inorganic perovskites, we speculate that the energy scale most relevant to the photovoltaic properties of the lead-halogen perovskites is set by the lead-halide bond, not by the hydrogen bond.
We study the circular photogalvanic effect in the organometal halide perovskite solar cell absorber CH$_3$NH$_3$PbI$_3$. For crystal structures which lack inversion symmetry, the calculated photocurrent density is about $10^{-9}$ A/W, comparable to the previously studied quantum well and bulk Rashba systems. Because of the dependence of the circular photogalvanic effect on inversion symmetry breaking, the degree of inversion asymmetry at different depths from the surface can be probed by tuning the photon energy and associated penetration depth. We propose that measurements of this effect may clarify the presence or absence of inversion symmetry, which remains a controversial issue and has been argued to play an important role in the high conversion efficiency of this material.