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Trimethylsilyl-substituted phosphines were treated with alkali metal tert-butyl alcoholates to prepare a series of highly reactive heavy alkali metal phosphides. Analyses of the phosphides revealed their polymeric ladder-type structure, containing four coordinate alkali metal centers and five coordinate phosphorus atoms. The retention of this structure type correlated with observed increase in reactivity, which can be related to the reduced steric shielding of the larger metal center by the ligand and donor.

Ionization in the condensed phase and molecular clusters leads to a complicated chain of processes with coupled electron-nuclear dynamics. It is difficult to describe such dynamics with conventional nonadiabatic molecular dynamics schemes since the number of states swiftly increases as the molecular system grows. It is therefore attractive to use a direct electron and nuclear propagation such as the real-time time-dependent density functional theory (RT-TDDFT). Here we report a RT-TDDFT benchmark study on simulations of singly and doubly ionized states of a water monomer and dimer as a prototype for more complex processes in a condensed phase. We employed the RT-TDDFT based Ehrenfest molecular dynamics with a generalized gradient approximate (GGA) functional and compared it with wave-function-based surface hopping (SH) simulations. We found that the initial dynamics of a singly HOMO ionized water dimer is similar for both the RT-TDDFT/GGA and the SH simulations but leads to completely different reaction channels on a longer time scale. This failure is attributed to the self-interaction error in the GGA functionals and it can be avoided by using hybrid functionals with large fraction of exact exchange (represented here by the BHandHLYP functional). The simulations of doubly ionized states are reasonably described already at the GGA level. This suggests that the RT-TDDFT/GGA method could describe processes following the autoionization processes such as Auger emission, while its applicability to more complex processes such as intermolecular Coulombic decay remains limited. [ABSTRACT FROM AUTHOR]

The optical spectrum of the hydrated(aqueous) electron, eaq–, is theprimary observable by means of which this species is detected, monitored,and studied. In theoretical calculations, this spectrum has most oftenbeen simulated using one-electron models. Here, we present ab initiosimulations of that spectrum in both bulk water and, for the firsttime, at the water/vapor interface, using density functional theoryand its time-dependent variant. Our results indicate that this approachprovides a reliable description, and quantitative agreement with theexperimental spectrum for the bulk species is obtained using a “tuned”long-range corrected functional. The spectrum of the interfacial electronis found to be very similar to the bulk spectrum. [ABSTRACT FROM AUTHOR]

The series of oligogermanes Pri3Ge(GePh2)nGePri3 (n = 0, 2; n = 1, 3; n = 2, 4; n = 3, 5) were prepared by the hydrogermolysis reaction. All four species were characterized by NMR (¹H and 13C) and UV/visible spectroscopy as well by cyclic voltammetry and differential pulse voltammetry. The oligogermanes exhibited a successive red shift in their absorbance maxima as the length of the Ge-Ge chain was increased, and these molecules also became easier to oxidize as the chain length was increased. The X-ray crystal structures of 4 and 5 as well as the trigermane HPh2GeGePh2GePh2H (6) were determined. The pentagermane 5 was shown to be dichroic in the solid state due to the packing of the individual molecules in a columnar fashion in the crystal. Pentagermane 5 is also luminescent in solution, exhibiting an emission maximum at 380 nm. The physical properties of 5, like the hexagermane Pri3Ge(GePh)4GePri3, mimic the properties of the larger polygermane systems. [ABSTRACT FROM AUTHOR]

We present an ab initio parametrization scheme for explicitly dipole-polarizable force fields for the simulation of molecular liquids. The scheme allows for, in principle, arbitrarily coarse-grained representations. All parameters in the force field are derived from first-principles, based on simple physical arguments. Only one fit parameter enters the parametrization, a global scaling factor for the size of the particles, which is adjusted to reproduce the experimental mass density. As important examples and for the first time, polarizable coarse-grained force fields are derived for 1-alkyl-3-methylimidazolium cations with varying alkyl-chain lengths (alkyl = ethyl, butyl, hexyl) and hexafluorophosphate and tetrafluoroborate anions. Our findings are in good agreement with experimental results and results of further atomistic simulations. Hence, the force fields can be faithfully used where polarizability is expected to play a significant role, such as simulations of energy storage devices.

Self-assembled phases based on monoglycerides are promising candidates for drug delivery systems. Alterations of these phases need to be performed by addition of substances which are biocompatible. Inverse bicontinuous cubic phases are altered by the addition of five amino acids, namely, glycine, phenylalanine, alanine, glutamine, and tryptophan. These natural molecules have a diversity of side chains which predicts their polarity and subsequently their interaction with the interfacial region. Whereas polar amino acids cause a slight shrinking of the fully hydrated phase, amino acids with a nonpolar side chain expand it. Tryptophan is also able to provoke a growth of inverse hexagonal, micellar cubic, and micellar structures. Amino acid concentrations in the aqueous phase, even above the amino acid's solubility, further affect all aforementioned structures and cause a significant enlargement of up to 26%. Besides the amino acids' impact on the structural sizes, they also affect the phase transition temperatures.

The hydrated electron is a crucial species in radiative processes, and it has been speculated that its behavior at the water surface could lead to specific interfacial chemical properties. Here, we address fundamental questions concerning the structure and energetics of an electron at the surface of water. We use the method of ab initio molecular dynamics, which was shown to provide a faithful description of solvated electrons in large water clusters and in bulk water. The present results clearly demonstrate that the surface electron is mostly buried in the interfacial water layer, with only about 10 % of its density protruding into the vapor phase. Consequently, it has a structure that is very similar to that of an electron solvated in the aqueous bulk. This points to a general feature of charges at the surface of water, namely, that they do not behave as half-dehydrated but rather as almost fully hydrated species.

The structure of the hydrated electron, which is a key species in radiative processes in water, has remained elusive. The traditional cavity model has been questioned recently, but the newly suggested picture of an electron delocalized over a region of enhanced water density is controversial. Here, we present results from ab initio molecular dynamics simulations, where not only the excess electron but also the valence electrons of the surrounding water molecules are described quantum mechanically. Unlike in previous one-electron pseudopotential calculations, many-electron interactions are explicitly accounted for. The present approach allows for partitioning of the electron solvated in liquid water into contributions from an inner cavity, neighboring water molecules, and a diffuse tail. We demonstrate that all three of these contributions are sizable and, consequently, important, which underlines the complex nature of the hydrated electron and warns against oversimplified interpretations based on pseudopotential models.

Understanding the properties of hydrated electrons, which were first observed using pulse radiolysis of water in 1962, is crucial because they are key species in many radiation chemistry processes. Although time-resolved spectroscopic studies and molecular simulations have shown that an electron in water (prepared, for example, by water photoionization) relaxes quickly to a localized, cavity-like structure ∼2.5 Å in radius, this picture has recently been questioned. In another experimental approach, negatively charged water clusters of increasing size were studied with photoelectron and IR spectroscopies. Although small water clusters can bind an excess electron, their character is very different from bulk hydrated species. As data on electron binding in liquid water have become directly accessible experimentally, the cluster-to-bulk extrapolations have become a topic of lively debate. Quantum electronic structure calculations addressing experimental measurables have, until recently, been largely limited to small clusters; extended systems were approached mainly with pseudopotential calculations combining a classical description of water with a quantum mechanical treatment of the excess electron. In this Account, we discuss our investigations of electrons solvated in water by means of ab initio molecular dynamics simulations. This approach, applied to a model system of a negatively charged cluster of 32 water molecules, allows us to characterize structural, dynamical, and reactive aspects of the hydrated electron using all of the system's valence electrons. We show that under ambient conditions, the electron localizes into a cavity close to the surface of the liquid cluster. This cavity is, however, more flexible and accessible to water molecules than an analogous area around negatively charged ions. The dynamical process of electron attachment to a neutral water cluster is strongly temperature dependent. Under ambient conditions, the electron relaxes in the liquid cluster and becomes indistinguishable from an equilibrated, solvated electron on a picosecond time scale. In contrast, for solid, cryogenic systems, the electron only partially localizes outside of the cluster, being trapped in a metastable, weakly bound "cushion-like" state. Strongly bound states under cryogenic conditions could only be prepared by cooling equilibrated, liquid, negatively charged clusters. These calculations allow us to rationalize how different isomers of electrons in cryogenic clusters can be observed experimentally. Our results also bring into question the direct extrapolation of properties of cryogenic, negatively charged water clusters to those of electrons in the bulk liquid. Ab initio molecular dynamics represents a unique computational tool for investigating the reactivity of the solvated electron in water. As a prototype, the electron-proton reaction was followed in the 32-water cluster. In accord with experiment, the molecular mechanism is a proton transfer process that is not diffusion limited, but rather controlled by a proton-induced deformation of the excess electron's solvent shell. We demonstrate the necessary ingredients of a successful density functional methodology for the hydrated electron that avoids potential pitfalls, such as self-interaction error, insufficient basis set, or lack of dispersion interactions. We also benchmark the density functional theory methods and outline the path to faithful ab initio simulations of dynamics and reactivity of electrons solvated in extended aqueous systems.