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Recent advances in computational chemistry now afford unprecedented opportunities to develop predictive capabilities that will lead to new photoswitchable alignment layer materials with low switching energies, enhanced bistability, write/erase fatigue resistance, and high-laser-damage thresholds. The near-IR laser-damage resistance of coumarin-based, photoalignment layers developed at the Laboratory for Laser Energetics has made it possible to fabricate a wide variety of photoaligned LC devices for high-peak-power laser applications, including wave plates, beam shapers, apodizers, and radial polarization converters.*

In the work described here, computational methods based on the density functional theory (DFT) and time-dependent density functional theory (TDDFT) were employed to determine the properties of a series of oligomeric methacrylate and acrylamide photoswitchable alignment layer materials intended as potential candidates for use in an optically switchable LC laser beam shaper. Twenty-two different terminal functional groups were computationally evaluated to determine their individual effects on the energy difference between the trans and cis isomerization-state energy levels (one of the three factors affecting bistability in photoswitchable alignment layers) when they were used as substituents on azobenzene cores linked through a four-carbon tether to methacrylate and acrylamide backbones. The effect of the alkyl tether connecting the chromophore to the oligomer backbone on the isomerization-state energy differences of the methacrylate and acrylamide oligomers was also investigated computationally. This work revealed the following key findings:

1. When methoxy-substituted azobenzene chromophores are tethered to a methacrylate oligomer, lower energy differences between the trans and cisisomerization states occur for alkyl tether lengths of 5, 6, 8, 9, and 11 carbons. The C₆ and C₁₁ tethers produce the smallest energy difference, implying that they are a good choice for a photoalignment coating intended for bistable switching applications. For the same core and an alkyl tether length of C₄, replacing the methoxy terminal group on the azobenzene core with alkyl groups up to C₉ appears to have limited ability to lower the isomerization-state energy difference, while cyanate ester and 2-methoxy-N-(2-methylphenyl) acetamide terminal groups are highly effective in producing the smallest differences in trans–cis isomerization energy levels.
2. Acrylamide oligomers tethered to a methoxy-substituted azobenzene chromophore show the smallest trans–cis isomerization energy differences for alkyl tethers containing 4, 5, 7, 8, and 9 carbon atoms, in some cases considerably smaller than those of the corresponding methacrylate oligomers. Unlike what was seen for methacrylate oligomers, replacing the methoxy group on the azobenzene core with C₅ and C₉ terminal alkyl groups shows a significant reduction in trans–cis isomerization-state energies. With the exception of C₄ and C₉ terminal groups, all of the acrylamide oligomers with alkyl-substituted azobenzene cores show consistently lower trans–cis isomerization energy state differences than do their methacrylate counterparts. Other terminal functional groups that show a large decrease in trans–cis isomerization-state energy differences are the 2-methoxy-N-(2-methylphenyl) acetamide group (62%) and the fluoroalkane terminal group (70%) as compared to an unsubstituted azobenzene core.
3. With only a few exceptions, acrylamide oligomers as a group exhibit lower trans–cis isomerization energy differences than methacrylate oligomers with the same structure, making them (in the absence of other factors) preferred candidates for photoswitchable device applications where good bistability is required.