Optical Kinetic Theory of Nonlinear Multimode Photonic Networks.

Recent experimental developments in multimode nonlinear photonic circuits (MMNPCs), have motivated the development of an optical thermodynamic theory that describes the equilibrium properties of an initial beam excitation. However, a nonequilibrium transport theory for these systems, when they are in contact with thermal reservoirs, is still terra incognita. Here, by combining Landauer and kinematics formalisms we develop a universal one-parameter scaling theory that describes the whole transport behavior from the ballistic to the diffusive regime, including both positive and negative optical temperature scenarios. We also derive a photonic version of the Wiedemann-Franz law that connects the thermal and power conductivities. Our work paves the way toward a fundamental understanding of the transport properties of MMNPCs and may be useful for the design of all-optical cooling protocols.

Temperature-driven narrowing of the insulating gap as a precursor of the insulator-to-metal transition: Implications for the electronic structure of solids.

We present a microscopic picture rationalizing the surprisingly steep decrease in the bandgap with temperature in insulators, crystalline or otherwise. The gap narrowing largely results from fluctuations of long-wavelength optical phonons-when the latter are present-or their disordered analogs if the material is amorphous. We elaborate on this notion to show that possibly with the exception of weakly bound solids made of closed-shell electronic configurations, the existence of an insulating gap or pseudogap in a periodic solid implies that optical phonons must be present, too. This means that in an insulating solid, the primitive cell must have at least two atoms and/or that a charge density wave is present, with the possible exception of weakly bonded solids such as rare-gas or ferromagnetic Wigner crystals. As a corollary, a (periodic) elemental solid held together by nonclosed shell interactions and whose primitive unit contains only one atom will ordinarily be a metal, consistent with observation. Consequences of the present picture for Wigner solids are discussed. A simple field theory of the metal-insulator transition is constructed that directly ties long-wavelength optical vibrations with fluctuations of an order parameter for the metal-insulator transition. The order parameter is shown to have at least two components, yet no Goldstone mode arises as a result of the transition.

Electronic torsional sound in linear atomic chains: Chemical energy transport at 1000 km/s.

We investigate entirely electronic torsional vibrational modes in linear cumulene chains. The carbon nuclei of a cumulene are positioned along the primary axis so that they can participate only in the transverse and longitudinal motions. However, the interatomic electronic clouds behave as a torsion spring with remarkable torsional stiffness. The collective dynamics of these clouds can be described in terms of electronic vibrational quanta, which we name torsitons. It is shown that the group velocity of the wavepacket of torsitons is much higher than the typical speed of sound, because of the small mass of participating electrons compared to the atomic mass. For the same reason, the maximum energy of the torsitons in cumulenes is as high as a few electronvolts, while the minimum possible energy is evaluated as a few hundred wavenumbers and this minimum is associated with asymmetry of zero point atomic vibrations. Theory predictions are consistent with the time-dependent density functional theory calculations. Molecular systems for experimental evaluation of the predictions are proposed.

Ballistic Energy Transport in Oligomers.

The development of nanocomposite materials with desired heat management properties, including nanowires, layered semiconductor structures, and self-assembled monolayer (SAM) junctions, attracts broad interest. Such materials often involve polymeric/oligomeric components and can feature high or low thermal conductivity, depending on their design. For example, in SAM junctions made of alkane chains sandwiched between metal layers, the thermal conductivity can be very low, whereas the fibers of ordered polyethylene chains feature high thermal conductivity, exceeding that of many pure metals. The thermal conductivity of nanostructured materials is determined by the energy transport between and within each component of the material, which all need to be understood for optimizing the properties. For example, in the SAM junctions, the energy transport across the metal-chain interface as well as the transport through the chains both determine the overall heat conductivity, however, to separate these contributions is difficult. Recently developed relaxation-assisted two-dimensional infrared (RA 2DIR) spectroscopy is capable of studying energy transport in individual molecules in the time domain. The transport in a molecule is initiated by exciting an IR-active group (a tag); the method records the influence of the excess energy on another mode in the molecule (a reporter). The energy transport time can be measured for different reporters, and the transport speed through the molecule is evaluated. Various molecules were interrogated by RA 2DIR: in molecules without repeating units (disordered), the transport mechanism was expected and found to be diffusive. The transport via an oligomer backbone can potentially be ballistic, as the chain offers delocalized vibrational states. Indeed, the transport regime via three tested types of oligomers, alkanes, polyethyleneglycols, and perfluoroalkanes was found to be ballistic, whereas the transport within the end groups was diffusive. Interestingly, the transport speeds via these chains were different. Moreover, the transport speed was found to be dependent on the vibrational mode initiating the transport. For the difference in the transport speeds to be explained, the chain bands involved in the wavepacket formation were analyzed, and specific optical bands of the chain were identified as the energy transporters. For example, the transport initiated in alkanes by the stretching mode of the azido end group (2100 cm(-1)) occurs predominantly via the CH2 twisting and wagging chain bands, but the transport initiated by the C=O stretching modes of the carboxylic acid or succinimide ester end groups occurs via C-C stretching and CH2 rocking bands of the alkane chain. Direct formation of the wavepacket within the CH2 twisting and wagging chain bands occurs when the transport is initiated by the N═N stretching mode (1270 cm-1) of the azido end-group. The transport via optical chain bands in oligomers involves rather large vibrational quanta (700-1400 cm(-1)), resulting in efficient energy delivery to substantial distances. Achieved quantitative description of various energy transport steps in oligomers, including the specific contributions of different chain bands, can result in a better understanding of the transport steps in nanocomposite materials, including SAM junctions, and lead towards designing systems for molecular electronics with a controllable energy transport speed.

Band-selective ballistic energy transport in alkane oligomers: toward controlling the transport speed.

Intramolecular transport of vibrational energy in two series of oligomers featuring alkane chains of various length was studied by relaxation-assisted two-dimensional infrared spectroscopy. The transport was initiated by exciting various end-group modes (tags) such as different modes of the azido (ν(N≡N) and ν(N═N)), carboxylic acid (ν(C═O)), and succinimide ester (νas(C═O)) with short mid-IR laser pulses. It is shown that the transport via alkane chains is ballistic and the transport speed is dependent on the type of the tag mode that initiates the transport. The transport speed of 8.0 Å/ps was observed when initiated by either ν(C═O) or νas(C═O). When initiated by ν(N≡N) and ν(N═N), the transport speed of 14.4 ± 2 and 11 ± 4 Å/ps was observed. Analysis of the vibrational relaxation channels of different tags, combined with the results for the group velocity evaluation, permits identification of the chain bands predominantly contributing to the transport for different cases of the transport initiation. For the transport initiated by ν(N≡N) the CH2 twisting and wagging chain bands were identified as the major energy transport channels. For the transport initiated by ν(C═O), the C-C stretching and CH2 rocking chain bands served as major energy transporters. The transport initiated by ν(N═N) results in direct formation of the wave packet within the CH2 twisting and wagging chain bands. These developments can aid in designing molecular systems featuring faster and more controllable energy transport in molecules.

Communication: fast transport and relaxation of vibrational energy in polymer chains.

We investigate ballistic vibrational energy transport through optical phonon band in oligomeric chains in the presence of decoherence. An exact solution is obtained for the excitation density in the space-time representation in the continuous limit and this solution is used to characterize the energy transport time and intensity. Three transport mechanisms are identified such as ballistic, diffusive, and directed diffusive regimes, occurring at different distances and time scales. The crossover between the two diffusive regimes is continuous, while the switch between the ballistic and diffusive mechanisms occurs in a discontinuous manner in accord with the recent experimental results on energy transport in perfluoroalkanes.

Temperature dependence of the ballistic energy transport in perfluoroalkanes.

Temperature dependence of intramolecular energy transport in perfluoroalkane oligomers with a chain length of 3-11 carbon atoms terminated by a carboxylic acid moiety on one end and a -CF2H group on another end was studied in solution experimentally and theoretically. Experiments were performed using a dual-frequency relaxation-assisted two-dimensional infrared spectroscopy method. The energy transport was initiated by exciting the C═O stretching mode of the acid and recorded by measuring a cross-peak amplitude between the C═O stretching and the C-H bending modes as a function of the waiting time between the excitation and probing. An efficient transport regime with a mean free path of 16.4 ± 2 Å is observed at 35 °C. The energy transport speed decreases at elevated temperatures, indicating a switch from the ballistic transport regime to diffusive. The modeling of the energy transport involving both ballistic and diffusive mechanisms is performed. It explains the temperature dependence of the energy transport speed and confirms a switch of the transport regime from ballistic at lower temperatures to diffusive at higher temperatures.

Nanoconstructions based on double-stranded nucleic acids.

We describe the formation and properties of nanoconstruction that consists of the double-stranded DNA molecules located at distance of 35-50 A in the spatial structure of particles of their cholesteric liquid-crystalline dispersions and cross-linked by artificial nanobridges. The resulting nanostructures possess the peculiar spatial and optical properties.