Theoretical Analysis of Properties of Ground and Excited States for Photodissociation of the C-O Bond in Polycarbonates.

Quantum chemical calculations were carried out to investigate the properties of the ground state (GS) and the excited state (ES) of bisphenol-A polycarbonate (PC) with bisphenol-A hydrogen carbonate (BPAHC) as a model compound. Time-dependent density functional theory (TDDFT) was used to obtain the absorption spectrum and the corresponding transition natures of BPAHC. Furthermore, the ESs related to the transitions of the carbonate group and neighboring phenyl ring were optimized employing the TDDFT method for photodegradation. Our results showed that the carbonate group is broken at an ES with relatively high energy, which has a significant C-O bond cleavage within the carbonate group compared to that of GS geometry. The carbonate group C-O bond cleavage is caused by two reasons. One is the transition from the O lone pair to the carbonate π anti-bonding which is commonly known, and the other one is the transition from the O lone pair to the phenyl group (adjacent to the carbonate group) π anti-bonding that is newly proposed.