Photoinduced Dynamics in Carbon Nanotube Aggregates Steered by Dark Excitons.

Only optically active excitons can be identified by transient absorption spectroscopy, and the actual mechanisms of exciton relaxation in nanoscale systems remain unknown as dipole-forbidden transitions and charge-transfer states are not accounted for. Focusing on interacting (6,4) and (8,4) carbon nanotubes (CNTs), we show that dark excitons largely determine the relaxation pathways for photogenerated excitons in CNT bundles. New channels appear involving asymmetric electron-hole excitations within the same CNT and charge-transfer states, in which the electron and hole are confined to separate CNTs.

Exciton multiplication from first principles.

Third-generation photovolatics require demanding cost and power conversion efficiency standards, which may be achieved through efficient exciton multiplication. Therefore, generating more than one electron-hole pair from the absorption of a single photon has vast ramifications on solar power conversion technology. Unlike their bulk counterparts, irradiated semiconductor quantum dots exhibit efficient exciton multiplication, due to confinement-enhanced Coulomb interactions and slower nonradiative losses.

Decoherence-induced surface hopping.

A simple surface hopping method for nonadiabatic molecular dynamics is developed. The method derives from a stochastic modeling of the time-dependent Schrödinger and master equations for open systems and accounts simultaneously for quantum mechanical branching in the otherwise classical (nuclear) degrees of freedom and loss of coherence within the quantum (electronic) subsystem due to coupling to nuclei. Electronic dynamics in the Hilbert space takes the form of a unitary evolution, intermittent with stochastic decoherence events that are manifested as a localization toward (adiabatic) basis states.

Electron attachment to the guanine-cytosine nucleic acid base pair and the effects of monohydration and proton transfer.

The guanine-cytosine (GC) radical anion and its interaction with a single water molecule is studied using ab initio and density functional methods. Z-averaged second-order perturbation theory (ZAPT2) was applied to GC radical anion for the first time. Predicted spin densities show that the radical character is localized on cytosine.

The role of surface defects in multi-exciton generation of lead selenide and silicon semiconductor quantum dots.

Multi-exciton generation (MEG), the creation of more than one electron-hole pair per photon absorbed, occurs for excitation energies greater than twice the bandgap (E(g)). Imperfections on the surface of quantum dots, in the form of atomic vacancies or incomplete surface passivation, lead to less than ideal efficiencies for MEG in semiconductor quantum dots. The energetic onset for MEG is computed with and without surface defects for nanocrystals, Pb(4)Se(4), Si(7), and Si(7)H(2).

Accurate Interaction Energies for Problematic Dispersion-Bound Complexes: Homogeneous Dimers of NCCN, P2, and PCCP.

All intermolecular interactions involve London dispersion forces. The accurate treatment of dispersion is essential for the computation of realistic interaction potentials. In general, the most reliable method for computing intermolecular interactions is coupled-cluster singles and doubles with perturbative triples [CCSD(T)] in conjunction with a sufficiently flexible Gaussian atomic orbital basis set, a combination which is not routinely applicable due to its excessive computational demands (CPU time, memory, storage).

Characterizing radiation-induced oxidation of DNA by way of the monohydrated guanine-cytosine radical cation.

The interaction of one water molecule with the guanine-cytosine radical cation has been studied with ab initio and density functional methods in order to help elucidate the nature of oxidized aqueous DNA. The theoretical spin density of [GC]*(+) reveals that the radical center is localized on guanine. The adiabatic ionization potential lowers from 7.

Remarkable features in the interactions of quadrupolar molecules.

Quadrupolar charge fields of molecules and of molecular fragments give rise to unique features in weakly interacting clusters and aggregations. Relative to dipole-dipole interactions, the interactions among quadrupolar molecules tend to allow for greater orientational distortions away from equilibrium. Potential surface regions have been found for several clusters that are attractive and yet very flat for certain directions.