Deep-red photoluminescent mechanoresponsive polymers with dynamic CuI-arylamide mechanophores.

We demonstrate the use of copper arylamide complexes as efficient photoluminescent mechanophores to design deep-red/near-IR emissive polymers showing reversible changes in photoluminescence intensity in the red/near-IR region in response to mechanical stretching. The mechanoresponse was repeatable over 30 cycles, showing a measurable increase of photoluminescence intensity even at a small applied stress of ca. 0.01 MPa. We demonstrate the potential of using conformationally dynamic copper amide complexes as sensitive and reversible mechanophores for near-IR imaging; systematic control over the emission range was achieved using amide modification.

Broadband and efficient adiabatic three-wave-mixing in a temperature-controlled bulk crystal.

Nonlinear interactions are commonly used to access to wavelengths not covered by standard laser systems. In particular, optical parametric amplification (OPA) is a powerful technique to produce broadly tunable light. However, common implementations of OPA suffer from a well-known trade-off, either achieving high efficiency for narrow spectra or inefficient conversion over a broad bandwidth. This shortcoming can be addressed using adiabatic processes. Here, we demonstrate a novel technique towards this direction, based on a temperature-controlled phase mismatch between the interacting waves. Using this approach, we demonstrate, by tailoring the temperature profile, an increase in conversion efficiency by 21%, reaching a maximum of 57%, while simultaneously expanding the bandwidth to over 300 nm. Our technique can readily enhance the performances of current OPA systems.

A photoinduced metal-like phase of monoclinic VO2 revealed by ultrafast electron diffraction.

The complex interplay among several active degrees of freedom (charge, lattice, orbital, and spin) is thought to determine the electronic properties of many oxides. We report on combined ultrafast electron diffraction and infrared transmissivity experiments in which we directly monitored and separated the lattice and charge density reorganizations that are associated with the optically induced semiconductor-metal transition in vanadium dioxide (VO2). By photoexciting the monoclinic semiconducting phase, we were able to induce a transition to a metastable state that retained the periodic lattice distortion characteristic of the semiconductor but also acquired metal-like mid-infrared optical properties. Our results demonstrate that ultrafast electron diffraction is capable of following details of both lattice and electronic structural dynamics on the ultrafast time scale.

Donor-Bridge-Acceptor Proton Transfer in Aqueous Solution.

We use ab initio molecular dynamics to study proton transfer in a donor-bridge-acceptor system in which the bridge is a single water molecule and the entire system is embedded in aqueous solution. The results, based on a large number of proton transfer trajectories, demonstrate that the dominant charge-transfer pathway is a subpicosecond "through bridge" event in which the bridge adopts an Eigen-like (hydronium) structure. We also identify another state in which the bridge forms a Zundel-like configuration with the acceptor that appears to be a dead end for the charge transfer. The reaction coordinate is inherently multidimensional and, as we demonstrate, cannot be given in terms of either local structural parameters of the donor-bridge-acceptor system or local solvent coordination numbers.

Concerted and Sequential Proton Transfer Mechanisms in Water-Separated Acid-Base Encounter Pairs.

The proton transfer mechanisms involved inside aqueous, solvent-separated encounter complexes between phenol and carboxyl moieties are studied using ab initio molecular dynamics and computational time-resolved vibrational spectroscopy. This model framework can be viewed as a ground-state analog of the excited-state proton transfer reactions that have been actively investigated using ultrafast spectroscopy. Three qualitatively distinct proton transfer pathways are observed in the simulations. These can be described as direct concerted, direct sequential, and through bulk transfers. The primary difference between the sequential and concerted mechanism is the involvement of a reaction intermediate in which the proton fluctuates for several picoseconds through the hydrogen bonds connecting donor and acceptor but resides primarily on an intervening water molecule in the encounter complex. These results contribute to our molecular level understanding of the diverse processes involved in proton transfer within water-separated encounter complexes.