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The thermomechanical response of organic semiconducting solids – an essential aspect to consider for the design of flexible electronics – was determined using terahertz vibrational spectroscopy and quantum quasiharmonic approximation simulations.

The thermomechanical response of organic semiconducting solids is an essential aspect to consider in the design of materials for advanced applications, and in particular, flexible electronics. The non-covalent intermolecular forces that exist in organic solids not only result in a diverse set of mechanical properties, but also a critical dependence of those same properties on temperature. However, studying the thermoelastic response of solids is experimentally challenging, often requiring large single-crystals and sensitive experimental apparatus. An alternative contactless approach involves using low-frequency vibrational spectroscopy to characterize the underlying intermolecular forces, and then combining this information with solid-state density functional theory simulations to retrieve the mechanical response of materials. This methodology leverages recent advances in the quasi-harmonic approximation to predict the temperature evolution of crystalline structures, dynamics, and associated forces, and then utilizes this information to determine the elastic tensor as a function of temperature. Here, this methodology is illustrated for two prototypical organic semiconducting crystals, rubrene and BTBT, and suggests a new alternative means to characterizing the thermoelastic response of organic materials.

Chromium-bearing tourmalines are rare. Chromium-rich tourmaline from the northwestern part of the Adirondack Mountains in the Adirondack Lowlands is among the most chromium-rich tourmalines found to date. The mineral, with >21.0 wt. % Cr2O3, is from the marble-hosted talc–tremolite–cummingtonite schist in the #1 mine in Balmat, St. Lawrence County, New York. The atomic arrangement of the sample (a = 16.0242(3) Å, c = 7.3002(2) Å) was refined to R1 = 0.0139. The composition, from chemical analyses and optimization of the formula, is X(Ca0.22Na0.69K0.01) Y(Cr3+1.68Mg0.80Ti0.13V0.06Mn0.02Fe0.02Li0.29) Z(Al3.11Cr3+1.18Mg1.70Fe0.01) T(Si5.93Al0.07) B3O27 OH3.99 F0.01. There has been extensive debate over the ordering of Cr3+ between the tourmaline Y and Z octahedral sites. Recent work has suggested that, at low concentrations (<~1.03 apfu), the substituent Cr3+ is ordered into the Y-site, whereas, at greater concentrations, the substituent is disordered over both octahedral sites. An analysis of nine recently published, high-precision structures of chromium-bearing tourmaline, in combination with the Adirondack tourmaline, suggests that structural changes to the Y-site at low concentrations of Cr3+ induce changes in the Z-site that make it more amenable to incorporation of the Cr3+ substituents by increasing <Z–O>. The bond lengths change to lower the bond-valence sum of Cr3+ in the Z-site of the chromium-dravite, making that site more amenable to the substituent. Calculations suggest that the Z-site begins to accept substituent Cr3+ when the bond valence sum of that ion in Z reduces to a value of ~3.36 valence units.