Abstract
Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation to the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications.
Highlights
Affected by these features[11,43]
We explore modifications of optical/electronic properties and photoinduced dynamics due to the insertion of an acene unit that breaks the circular symmetry of CPP
We have modeled three [10]CPPs molecules with inserted naphthalene (CPPN), anthracene (CPPA), and tetracene (CPPT) units
Summary
Affected by these features[11,43]. Besides, the insertion of other organic compounds between phenyls, like alkyl chains[44] and acene units[45,46,47], has a significant impact in their optical properties and it can, eventually, lead a gradual modulation of the length scale of exciton localization (self-trapping). We explore modifications of optical/electronic properties and photoinduced dynamics due to the insertion of an acene unit that breaks the circular symmetry of CPP. The acene units gradually break this symmetry, introduce localized electronic states and significantly alter optical selection rules[62]. The lowest excited state being optically forbidden in ideal structures, gains a significant transition dipole moments oriented along acene’s short axis. Such transformations of electronic structure has characteristic footprints in photoexcited non-radiative relaxation as shown with our non-adiabatic excited-state molecular dynamics (NA-ESMD)[63,64] simulations. Accompanying vibrational energy relaxation and redistribution are rationalized by examining bond-length alternation parameters and torsional motions
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