Covalent Linking Greatly Enhances Photoinduced Electron Transfer in Fullerene-Quantum Dot Nanocomposites: Time-Domain Ab Initio Study.

Nonadiabatic molecular dynamics combined with time-domain density functional theory are used to study electron transfer (ET) from a CdSe quantum dot (QD) to the C60 fullerene, occurring in several types of hybrid organic/inorganic nanocomposites. By unveiling the time dependence of the ET process, we show that covalent bonding between the QD and C60 is particularly important to ensure ultrafast transmission of the excited electron from the QD photon-harvester to the C60 electron acceptor. Despite the close proximity of the donor and acceptor species provided by direct van der Waals contact, it leads to a notably weaker QD-C60 interaction than a lengthy molecular bridge. We show that the ET rate in a nonbonded mixture of QDs and C60 can be enhanced by doping. The photoinduced ET is promoted primarily by mid- and low-frequency vibrations. The study establishes the basic design principles for enhancing photoinduced charge separation in nanoscale light harvesting materials.

Confinement by carbon nanotubes drastically alters the boiling and critical behavior of water droplets.

Vapor pressure grows rapidly above the boiling temperature, and past the critical point liquid droplets disintegrate. Our atomistic simulations show that this sequence of events is reversed inside carbon nanotubes (CNT). Droplets disintegrate first and at low temperature, while pressure remains low. The droplet disintegration temperature is independent of the CNT diameter. In contrast, depending on CNT diameter, a temperature that is much higher than the bulk boiling temperature is required to raise the internal pressure. The control over pressure by CNT size can be useful for therapeutic drug delivery.

Vibrational energy transfer between carbon nanotubes and nonaqueous solvents: a molecular dynamics study.

We report molecular dynamics (MD) simulation of energy exchange between single-walled carbon nanotubes (CNTs) and two aprotic solvents, acetonitrile and cyclohexane. Following our earlier study of hydrated CNTs, we find that the time scales and molecular mechanisms of the energy transfer are largely independent of the nature of the surrounding medium, and therefore, should hold for other media including polymer matrices and DNA. The vibrational energy exchange between CNT and solvents exhibits two time-scales. Over half of the energy is transferred in less than one picosecond, indicating that the dominant exchange mechanism is inertial relaxation. It occurs by collisions of solvent molecules with CNT walls, facilitated by the short-range Lennard-Jones interaction. Additional several picoseconds are required for the remainder of the vibrational energy exchange, corresponding to the diffusive relaxation mechanism and involving collective molecular motions. The faster stage of the CNT-solvent energy exchange occurs on the same time-scale, and therefore, competes with the vibrational energy relaxation inside CNTs. The energy exchange time-scales are significantly influenced by the arrangement of solvent molecules inside CNTs. Generally, the effects of confinement on the dynamics can be rationalized by analysis of the solvent structure. For the same CNT diameter, the extent of the confinement effect strongly depends on the size of the solvent molecules. Icelike properties in water seen in small CNTs disappear in CNTs with intermediate diameters. In acetonitrile and cyclohexane, medium size CNTs still show strong confinement effects. Rotational motions of acetonitrile molecules are inhibited, and the cyclohexane density is dramatically decreased. The disbalance between the local temperatures of the inside and outside regions of the solvent equilibrates through a tube-mediated interaction, rather than by a direct coupling between the two solvent subsystems. In all cases, the CNT-solvent energy transfer is mediated by slow motions in the frequency range of CNT radial breathing modes.

Solute-solvent interactions determine the effect of external electric field on the intensity of molecular absorption spectra.

The study of the electronic absorption spectra of 4-aminoazobenzene subjected to an external electric field in nonpolar and polar solvents shows that the field-induced change in the absorption intensity is dominated by the solvent-solute interaction. Moreover, solvent can determine the sign of the change of the absorption intensity. These experimental observations are supported by ab initio electronic structure calculations and are rationalized by analytic theory. The results carry particular importance for the numerous fundamental and practical applications of electric fields to understanding and design of new materials and biological systems.

Dynamics of the photoexcited electron at the chromophore-semiconductor interface.

Electron dynamics at molecular-bulk interfaces play a central role in a number of different fields, including molecular electronics and sensitized semiconductor solar cells. Describing electron behavior in these systems is difficult because it requires a union between disparate interface components, molecules and solid-state materials, that are studied by two different communities, chemists and physicists, respectively. This Account describes recent theoretical efforts to bridge that gap by analyzing systems that serve as good general models of the interfacial electron dynamics. The particular systems that we examine, dyes attached to TiO2, are especially important since they represent the key component of dye-sensitized semiconductor solar cells, or Gratzel cells. Gratzel cells offer a cheap, efficient alternative to traditional Si-based solar cells. The chromophore-TiO2 interface is a remarkably good target for theorists because it has already been the subject of many excellent experimental investigations. The electron dynamics in the chromophore-semiconductor systems are surprisingly rich and involve a great variety of processes as illustrated in the scheme above. The exact rates and branching ratios depend on the system details, including the semiconductor type, its bulk phase, and its exposed surface, the chromophore type, the presence or absence of a chromophore-semiconductor bridge, the alignment of the chromophore and semiconductor energy levels, the surface termination, the active vibrational modes, the solvent, the type of electrolyte, the presence of surface defects, etc. Still, the general principles governing the electron dynamics at the bulk-semiconductor interface can be understood and formulated by considering a few specific examples. The ultrafast time scale of the electronic and vibrational processes at the molecule-bulk interface make it difficult to invoke traditional theories. Instead, we perform explicit time-domain simulations with an atomistic representation of the interface. This approach most directly mimics the time-resolved experimental data and provides a detailed description of the processes as they occur in real time. The simulations described in this Account take into consideration the chemical structure of the system, determine the role of the vibrational motion and non-adiabatic coupling, uncover a vast variety of electron dynamics scenarios, and ultimately, allow us to establish the basic criteria that provide an understanding of this complicated physical process. The insights attained in the theoretical studies let us formulate a number of practical suggestions for improving the properties of the dye-sensitized semiconductor solar cell and for controlling the electron transfer across molecular-bulk interfaces.