Evidence for photoinduced electron transfer from the excited state of a conducting polymer onto buckminsterfullerene, C(60), is reported. After photo-excitation of the conjugated polymer with light of energy greater than the pi-pi* gap, an electron transfer to the C(60) molecule is initiated. Photoinduced optical absorption studies demonstrate a different excitation spectrum for the composite as compared to the separate components, consistent with photo-excited charge transfer. A photoinduced electron spin resonance signal exhibits signatures of both the conducting polymer cation and the C(60) anion. Because the photoluminescence in the conducting polymer is quenched by interaction with C(60), the data imply that charge transfer from the excited state occurs on a picosecond time scale. The charge-separated state in composite films is metastable at low temperatures.
In this and the accompanying paper [L. Smilowitz et al., J. Chem. Phys. 117, 3789, 2002] we present a theoretical treatment and experimental study, respectively, of the β–δ solid state phase transition in the organic nitramine molecule octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The transition is thermodynamically first order with a measured latent heat, occurs via nucleation and growth, and exhibits a thermally activated rate of transformation. We construct a two state kinetic model of the system consisting of equilibrium terms first order in the β or δ mole fraction simulating nucleation, and second order in β and δ simulating growth. The model has four rate constants, the temperature dependence of which is described by eight parameters. We use the transition state formulation of the rate constants and apply a thermodynamic model of the activated state that associates the difference in activated state free energy in forward and reverse directions with the equilibrium transition free energy, and identifies the activated state of the growth process with a metastable melt. By associating components of the activated state free energy with independently measured thermodynamic energies we reduce the degrees of freedom to three, which we fix initially by comparison with previously published kinetic data. We apply the model to both the β–δ and δ–β transformations over a temperature range from 300 to 700 K in order to assess the theoretical validity of the model. The model reproduces the half time of the transition over this entire range, spanning conversion times from 106 to 10−4 s. In the accompanying paper we present an experimental study of the kinetics and mechanism of the phase transition based on second harmonic generation spectroscopy. We use second harmonic generation to verify the nucleation and growth mechanism of the transition and measure the mole fraction change with time over a wide range of temperatures. We use the set of parameters established by theoretical considerations in this paper as an initial parameter set and determine an optimized set by comparison with these data.
A new phenomenon is theoretically predicted, namely, that solid-solid transformation with a relatively large transformation strain can occur through virtual melting along the interface at temperatures significantly (more than 100 K) below the melting temperature. The energy of elastic stresses, induced by transformation strain, increases the driving force for melting and reduces the melting temperature. Immediately after melting, the stresses relax and the unstable melt solidifies. Fast solidification in a thin layer leads to nanoscale cracking, which does not affect the thermodynamics and kinetics of solid-solid transformation. Seven theoretical predictions are in quantitative agreement with experiments conducted on the beta-->delta transformation in the HMX energetic crystal.
In this paper we present second harmonic generation (SHG) experiments designed to confirm the mechanism and quantify the transformation kinetics of the β–δ solid state phase transition in the organic nitramine molecule octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The β phase adopts a centrosymmetric crystallographic configuration (P21/c) while the δ phase adopts a noncentrosymmetric one (P61(P65)). As expected, this results in a very poor generation of SHG intensity from the β phase, while the δ phase is very efficient, rivaling KH2PO4 in absolute efficiency. SHG thus provides a very high sensitivity zero background probe of the δ phase. We discuss the use of this signal as a quantitative measure of the δ phase mole fraction in ensembles of free HMX crystals and crystals embedded in a visco–elastic polymer matrix. We report imaging experiments where the spatial characteristics of the transformation are shown to be consistent with nucleation from a low density of initial sites, followed by rapid growth. We also report experiments where the total integrated SHG is measured and used to infer the transition progress as a function of time in a series of isothermal experiments on both β–δ conversion and δ–β reversion. Additionally, reversibility experiments are reported which are used to verify both the volumetric mechanism of SHG generation in this system and the independence of these results to the internal stress state of the polycrystalline samples. We compare the measured SHG intensity as a function of time for a range of temperatures with predictions of the two state kinetic model presented in the accompanying paper [B. F. Henson et al., J. Chem. Phys. 117, 3780 (2002)]. We perform a set of parameter optimization calculations based on agreement with the predictions of the model. Optimization does not significantly change the kinetic parameters that are thermodynamically constrained by the model, but there is a distribution of parameters necessary to reproduce the nucleation kinetics observed. In particular, a striking difference in nucleation kinetics is observed between samples of free crystals and crystals embedded in a visco–elastic polymer matrix.
We theoretically predict a new phenomenon, namely, that a solid-solid phase transformation (PT) with a large transformation strain can occur via internal stress-induced virtual melting along the interface at temperatures significantly (more than 100 K) below the melting temperature. We show that the energy of elastic stresses, induced by transformation strain, increases the driving force for melting and reduces the melting temperature. Immediately after melting, stresses relax and the unstable melt solidifies. Fast solidification in a thin layer leads to nanoscale cracking which does not affect the thermodynamics or kinetics of the solid-solid transformation. Thus, virtual melting represents a new mechanism of solid-solid PT, stress relaxation, and loss of coherence at a moving solid-solid interface. It also removes the athermal interface friction and deletes the thermomechanical memory of preceding cycles of the direct-reverse transformation. It is also found that nonhydrostatic compressive internal stresses promote melting in contrast to hydrostatic pressure. Sixteen theoretical predictions are in qualitative and quantitative agreement with experiments conducted on the PTs in the energetic crystal HMX. In particular, (a) the energy of internal stresses is sufficient to reduce the melting temperature from 551 to 430 K for the delta phase during the beta --> delta PT and from 520 to 400 K for the beta phase during the delta --> beta PT; (b) predicted activation energies for direct and reverse PTs coincide with corresponding melting energies of the beta and delta phases and with the experimental values; (c) the temperature dependence of the rate constant is determined by the heat of fusion, for both direct and reverse PTs; results b and c are obtained both for overall kinetics and for interface propagation; (d) considerable nanocracking, homogeneously distributed in the transformed material, accompanies the PT, as predicted by theory; (e) the nanocracking does not change the PT thermodynamics or kinetics appreciably for the first and the second PT beta <--> delta cycles, as predicted by theory; (f) beta <--> delta PTs start at a very small driving force (in contrast to all known solid-solid transformations with large transformation strain), that is, elastic energy and athermal interface friction must be negligible; (g) beta --> alpha and alpha --> beta PTs, which are thermodynamically possible in the temperature range 382.4 < theta < 430 K and below 382.4 K, respectively, do not occur.
We present studies of steady-state photoinduced absorption (PIA) spectroscopy on photoexcitations in a series of well-defined a-oligothiophene (T,, , n=6, 7, 9, and 11) films and solutions. The PIA spectra and the excited state lifetimes are consistent with the signatures of a photoexcited triplet state. The PIA spectra consist of a strong vibronically resolved subgap absorption, which is readily observed in solid-state films and in solutions at ambient and cryogenic temperatures. The transition energy is linearly dependent on the reciprocal chain length and shifts to lower energy for longer oligomers. Variation of the modulation frequency and the pump intensity under matrix-isolated conditions reveals that the photoexcitation is created via an intrachain mechanism and decays nonradiatively with monomolecular kinetics. In solid films we find a significant contribution of a bimolecular decay process to the relaxation rate.
We present the results of time-resolved luminescence studies of poly[2-methoxy, 5-(2′-ethyl-hexyloxy)-p-phenylene-vinylene] (MEH-PPV), as a pure film, in solution, in a gel formed by a network of ultrahigh molecular weight polyethylene (UHMW-PE), and in a blend with UHMW-PE. The luminescence has a characteristic lifetime of 200–300 ps at room temperature, increasing to 500–700 ps when the materials are cooled to 80 K; the decay time is approximately the same for all the physical forms of the material (solution, film, gel, blend). The relatively short lifetimes, compared to intrinsic values calculated from absorption and emission spectra, and the observed temperature dependence indicate that the luminescence decay is quenched by nonradiative processes. The time decay of the photoluminescence deviates from a single exponential for most forms of the MEH-PPV. Best fits to stretched exponential and double exponential expressions are presented. Steady state photoluminescence spectra and integrated luminescence vs pump intensity data are presented in order to establish which of the possible mechanisms are most important.
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