Quantum Coherence Governs Macroscopic Polymorphism in Organic Semiconductors

Abstract

Polymorphism in organic semiconductors is conventionally framed as equilibrium thermodynamic selection, yet atmospheric-pressure vapor deposition routinely produces metastable phases that defy classical nucleation theory. We develop a symmetry-resolved open quantum system formulation of quantum dissipative assembly (QDA), in which the fundamental assembly unit is a vibronic wavepacket whose internal degrees of freedom are classified by the irreducible representations of the molecular point group. The carrier-gas environment acts as a structured dissipative bath with irrep-resolved spectral densities, and polymorph selection corresponds to relaxation into a symmetry-resolved maximum-transmittance attractor (MTA) rooted in quantum scattering theory and impedance matching. Guided by this theory, we tune the carrier-gas dissipative environment via reactor geometry, flow velocity, and precursor concentration to selectively synthesize a previously unreported polar polymorph of copper phthalocyanine, omega-CuPc, crystallizing in space group P2 with a dimerized bilayer superstructure and an extreme Davydov splitting of 154 nm. Further structural refinement with a 4-molecule modulated supercell model resolves the majority of discrepancies between powder X-ray diffraction and energy minimization, revealing secondary layer orientation modulation as a higher-order dissipative optimization product. The framework consistently explains the formation windows of the eta, alpha, and beta polymorphs, their distinct morphologies, and the marked difference in crystalline order between open-shell CuPc and closed-shell NiPc. Our findings establish a symmetry-guided, environment-controlled polymorph engineering strategy rooted in QDA, where the carrier-gas atmosphere serves as an active dissipative medium shaping the symmetry-resolved dissipative landscape rather than acting as an inert thermal bath.

22 pages,5 figures