Mechanical flexibility in single crystals of covalently bound materials is a fascinating and poorly understood phenomenon. We present here the first example of a plastically flexible one‐dimensional (1D) coordination polymer. The compound [Zn(μ‐Cl)2(3,5‐dichloropyridine)2]n is flexible over two crystallographic faces. Remarkably, the single crystal remains intact when bent to 180°. A combination of microscopy, diffraction, and spectroscopic studies have been used to probe the structural response of the crystal lattice to mechanical bending. Deformation of the covalent polymer chains does not appear to be responsible for the observed macroscopic bending. Instead, our results suggest that mechanical bending occurs by displacement of the coordination polymer chains. Based on experimental and theoretical evidence, we propose a new model for mechanical flexibility in 1D coordination polymers. Moreover, our calculations propose a cause of the different mechanical properties of this compound and a structurally similar elastic material.
Sum frequency generation (SFG) and low-energy electron diffraction (LEED) have been used to revisit CO adsorption on Pd(100) from very low coverages up to saturation at 300 K. Below 0.5 ML, variations of SFG frequency and intensity with coverage are consistent with IRAS results from the literature. Novel observations are done above 0.5 ML, where the CO adlayer compression takes place. The existing compression model postulates the coexistence of compressed and uncompressed CO. We observe two bands in the spectral region of bridge sites and assign them to compressed and uncompressed CO. Both types of CO behave very differently: the molecular hyperpolarizability at compressed sites is smaller by a factor of 2 than at uncompressed sites. The frequency of uncompressed CO red-shifts during compression as the partial coverage decreases, while that of compressed CO continues to blue-shift as coverage increases. In the time domain, the coexistence of compressed and uncompressed sites results in oscillations in the decay of SFG intensity. A strong decrease from 690 to 222 fs of the phase relaxation time of uncompressed CO is observed during compression, indicating a stronger coupling to the substrate. These results are complemented by calculations of dipole−dipole interactions and DFT VASP calculations. While continuing blue-shift of compressed sites reflects a combination of increasing dipolar coupling and chemisorption change with coverage like below 0.5 ML, the very large red-shift amplitude of uncompressed CO indicates a large chemical contribution opposite to compressed CO. DFT VASP calculations allow us to follow the surface structure evolution from 0.5 to 0.67 ML and CO frequency changes with coverage. Pd atoms below compressed CO rows are pushed up, and compressed CO is tilted by 8− 9°with respect to the surface normal. A frequency split between compressed and uncompressed CO is found in agreement with experimental data. These results suggest that while compressed CO is less strongly bonded as compression proceeds the remaining uncompressed CO is more strongly bonded.
The evolution of the MgO(001) film morphology on Ag(001) was studied in dependence on the growth temperature (373À673 K) and grown MgO quantity (0.2À2 ML) by lowenergy electron diffraction and scanning tunneling microscopy. We evidence an island growth mode of MgO for all temperatures. At 373 K, the MgO film exhibits a high island density, which is due to a too small surface mobility of the film compounds during the film growth. At a growth temperature of 673 K, silver hampers a perfect growth of MgO islands due to its high mobility, which leads to dendrites of MgO. The flattest and largest MgO islands are obtained at a growth temperature of around 573 K, which is a compromise guaranteeing a sufficiently high Mg or MgO mobility but also an enough low diffusion of silver.
Liquid
water at ambient temperature displays ultrafast molecular
motions and concomitant fluctuations of very strong electric fields
originating from the dipolar H
2
O molecules. We show that
such random intermolecular fields induce the tunnel ionization of
water molecules, which becomes irreversible if an external terahertz
(THz) pulse imposes an additional directed electric field on the liquid.
Time-resolved nonlinear THz spectroscopy maps charge separation, transport,
and localization of the released electrons on a few-picosecond time
scale. The highly polarizable localized electrons modify the THz absorption
spectrum and refractive index of water, a manifestation of a highly
nonlinear response. Our results demonstrate how the interplay of local
electric field fluctuations and external electric fields allows for
steering charge dynamics and dielectric properties in aqueous systems.
Metal–organic overlayer structures formed by 1,4-phenylene-diisocyanide (PDI) and Au adatoms on Au(111) in UHV, their stability in air, and the tip-induced Au nanoparticle formation on PDI–Au(111) surfaces in air were investigated using scanning tunneling microscopy (STM) and vibrational spectroscopy. This study reveals that the distribution of Au nanoparticles created during tip-induced release of Au atoms from molecule-Au adatom complexes shows strong dependence on the PDI coverage. Ordered Au nanoparticle arrays form in the medium-coverage regime, while more disordered distributions are observed at low and saturation coverages. The different distributions of Au nanoparticles are a direct consequence of the coverage-dependent assembly of (PDI–Au)n chains, their different stability in air, and a templating effect of the Au(111) surface, which is most pronounced for medium coverage, where phases of densely packed (PDI–Au)n chains and disordered PDI–Au assemblies are confined, respectively, to the fcc and hcp regions of the (22 × √3) surface reconstruction of Au(111). The Au nanoparticles nucleate preferentially in the disordered or defective regions of the PDI–Au precursor overlayer, and their formation requires ambient air and high negative tip-bias, suggesting an electrochemical initiation of Au release from the molecule–Au adatom complexes
Confinement of hot electrons in metal nanoparticles (NPs) is expected to lead to increased reactivity in heterogeneous catalysis. NP size as well as support may influence molecule-NP coupling. Here, we use ultrafast nonlinear vibrational spectroscopy to follow energy transfer from hot electrons generated in Pd NP/MgO/Ag(100) to chemisorbed CO. Photoexcitation and photodesorption occur on an ultrashort time scale and are selective according to adsorption site. When the MgO layer is thick enough, it becomes NP size-dependent. Hot electron confinement within NPs is unfavorable for photodesorption, presumably because its dominant effect is to increase relaxation to phonons. An avenue of research is open where NP size and support thickness, photon energy, and molecular electronic structure will be tuned to obtain either molecular stability or reactivity in response to photon excitation.
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