Svetlana Kilina

Effect of Surface Ligands on Optical and Electronic Spectra of Semiconductor Nanoclusters

We investigate the impact of ligands on the morphology, electronic structure, and optical response of the Cd(33)Se(33) cluster, which overlaps in size with the smallest synthesized CdSe nanocrystal quantum dots (QDs). Our density functional theory calculations demonstrate significant surface reorganization for both the bare cluster and the cluster capped with amine or phosphine oxide model ligands. We observe strong surface-ligand interactions leading to substantial charge redistribution and polarization effects on the surface. These effects result in the development of hybridized states, for which the electronic density is spread over the cluster and the ligands. The loss of one of the passivating ligands leads to either optically dark or bright additional states inside of the band gap, depending on the position of the leaving ligand on the QD surface. However, for fully ligated QDs, neither the ligand-localized nor hybridized molecular orbitals appear as trap states inside or near the band gap of the QD. Instead, being mostly optically dark, dense hybridized states could open new relaxation channels for high-energy photoexcitations. Comparing QDs passivated by different ligands, we also found that hybridized states are denser at the edge of the conduction band of the cluster ligated with phosphine oxide molecules than that with primary amines. Such a different manifestation of ligand binding may potentially lead to faster electron relaxation in QDs passivated by phosphine oxide than by amine ligands.

Breaking the Phonon Bottleneck in PbSe and CdSe Quantum Dots: Time- Domain Density Functional Theory of Charge Carrier Relaxation

Spatial confinement can create relaxation bottlenecks by mismatch between electronic and vibrational frequencies. This hypothesis motivated discovery of multiple excitons, which could greatly enhance the efficiency of quantum dot (QD) solar cells. Surprisingly, recent experiments showed no bottleneck. Our time-domain ab initio study of the electron-phonon dynamics rationalizes the fast relaxation in PbSe and CdSe QDs, which have substantially different electronic properties. Atom fluctuations and surface effects lift degeneracies and create dense distributions of electronic levels at all but the lowest energies, while confinement enhances the electron-phonon coupling. The analysis applies to nanomaterials in general, modifying the fundamental view on the electron-phonon interaction.

Scanning tunneling microscopy of DNA-wrapped carbon nanotubes.

We employ scanning tunneling microscopy (STM) to reveal the structure of DNA-carbon nanotube complexes with unprecedented spatial resolution and compare our experimental results to molecular dynamics simulations. STM images show strands of DNA wrapping around (6,5) nanotubes at approximately 63 degrees angle with a coiling period of 3.3 nm, in agreement with the theoretical predictions. In addition, we observe width modulations along the DNA molecule itself with characteristic lengths of 1.9 and 2.5 nm, which remain unexplained. In our modeling we use a helical coordinate system, which naturally accounts for tube chirality along with an orbital charge density distribution and allows us to simulate this hybrid system with the optimal pi-interaction between DNA bases and the nanotube. Our results provide novel insight into the self-assembling mechanisms of nanotube-DNA hybrids and can be used to guide the development of novel DNA-based nanotube separation and self-assembly methods, as well as drug delivery and cancer therapy techniques.

Surface Ligands Increase Photoexcitation Relaxation Rates in CdSe Quantum Dots

Understanding the pathways of hot exciton relaxation in photoexcited semiconductor nanocrystals, also called quantum dots (QDs), is of paramount importance in multiple energy, electronics and biological applications. An important nonradiative relaxation channel originates from the nonadiabatic (NA) coupling of electronic degrees of freedom to nuclear vibrations, which in QDs depend on the confinement effects and complicated surface chemistry. To elucidate the role of surface ligands in relaxation processes of nanocrystals, we study the dynamics of the NA exciton relaxation in Cd(33)Se(33) semiconductor quantum dots passivated by either trimethylphosphine oxide or methylamine ligands using explicit time-dependent modeling. The large extent of hybridization between electronic states of quantum dot and ligand molecules is found to strongly facilitate exciton relaxation. Our computational results for the ligand contributions to the exciton relaxation and electronic energy-loss in small clusters are further extrapolated to larger quantum dots.

Light-Driven and Phonon-Assisted Dynamics in Organic and Semiconductor Nanostructures

Semiconductor Nanostructures Svetlana Kilina,† Dmitri Kilin,‡ and Sergei Tretiak* †Chemistry and Biochemistry Department, North Dakota State University, Fargo, North Dakota 5810, United States ‡Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, United States Theoretical Division, Center for Nonlinear Studies (CNLS) and Center for Integrated Nanotechnologies (CINT), Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States

Electronic Structure of Self-Assembled Amorphous Polyfluorenes

We investigate the role of conformational disorder and intermolecular interactions on the electronic structure of amorphous clusters of polyfluorenes. Classical molecular dynamics simulations are used to determine probable molecular geometries and chain packing, and first-principles density functional theory calculations are employed to determine electronic structure and orbital localization properties. Intramolecular and intermolecular effects are disentangled by contrasting results for densely packed oligomer clusters and for ensembles of isolated oligomers with the same intramolecular geometries. Our simulations show that intermolecular disorder allows for nearly planar configurations of interacting fluorenes compared to the isolated molecules. This rationalizes the experimentally detected formation of the planar crystalline morphologies that frequently accompany twisted glassy configurations in fluorene films. The energy gap (HOMO-LUMO gap) significantly decreases for planar configurations. The electron and hole orbital energies are strongly dependent on both torsional angles and intermolecular interactions. This leads to strong localization of electronic states in amorphous polymer aggregates, which is analyzed by examining the respective orbital participation ratios. Notably, the energies of unoccupied levels show stronger dependence on the conformational disorder, compared to that of occupied levels. This results in the more probable formation of trap states near the edge of the conduction band than near the valence band.

Electronic Fingerprints of DNA Bases on Graphene

We calculate the electronic local density of states (LDOS) of DNA nucleotide bases (A,C,G,T), deposited on graphene. We observe significant base-dependent features in the LDOS in an energy range within a few electronvolts of the Fermi level. These features can serve as electronic fingerprints for the identification of individual bases in scanning tunneling spectroscopy (STS) experiments that perform image and site dependent spectroscopy on biomolecules. Thus the fingerprints of DNA-graphene hybrid structures may provide an alternative route to DNA sequencing using STS.

Brightening of the lowest exciton in carbon nanotubes via chemical functionalization.

Using time-dependent density functional theory, we found that chemical functionalization at low concentrations of single-walled carbon nanotubes (SWNTs) locally alters the π-conjugated network of the nanotube surface and leads to a spatial confinement of the electronically excited wave functions. Depending on the adsorbant positions, the chemisorption significantly modifies the optical selection rules. Our modeling suggests that photoluminescent efficiency of semiconducting SWNT materials can be controlled by selective chemical functionalization.

Photoinduced Conductivity of a Porphyrin−Gold Composite Nanowire†

Negatively charged phosphine groups on the backbone of DNA are known to attract gold nanoclusters from a colloid, assembling the clusters at fixed intervals. Bridging these intervals with porphyrin-dye linkers forms an infinite conducting chain, a quantum wire whose carrier mobility can be enhanced by photoexcitation. The resulting nanoassembly can be used as a gate: a wire with a controllable conductivity. The electronic structure of the porphyrin-gold wire is studied here by density functional theory, and the conductivity of the system is determined as a function of the photoexcitation energy. Photoexcitations of the dye are found to enhance the wire conductivity by orders of magnitude.

Cross-polarized excitons in carbon nanotubes

Polarization of low-lying excitonic bands in finite-size semiconducting single-walled carbon nanotubes (SWNTs) is studied by using quantum-chemical methodologies. Our calculations elucidate properties of cross-polarized excitons, which lead to the transverse optical absorption of nanotubes and presumably couple to intermediate-frequency modes recently observed in resonance Raman excitation spectroscopy. We identify up to 12 distinct excitonic transitions below the second fundamental band associated with the E22 van Hove singularity. Calculations for several chiral SWNTs distinguish the optically active “bright” excitonic band polarized parallel to the tube axis and several optically “weak” cross-polarized excitons. The rest are optically (near) forbidden “dark” transitions. An analysis of the transition density matrices related to excitonic bands provides detailed information about delocalization of excitonic wavefunction along the tube. Utilization of the natural helical coordinate system accounting for the tube chirality allows one to disentangle longitudinal and circumferential components. The distribution of the transition density matrix along a tube axis is similar for all excitons. However, four parallel-polarized excitons associated with the E11 transition are more localized along the circumference of a tube, compared with others related to the E12 and E21 cross-polarized transitions. Calculated splitting between optically active parallel- and cross-polarized transitions increases with tube diameter, which compares well with experimental spectroscopic data.