Ultrafast Exciton Self-Trapping upon Geometry Deformation in Perylene-Based Molecular Aggregates.

Femtosecond time-resolved experiments demonstrate that the photoexcited state of perylene tetracarboxylic acid bisimide (PBI) aggregates in solution decays nonradiatively on a time-scale of 215 fs. High-level electronic structure calculations on dimers point toward the importance of an excited state intermolecular geometry distortion along a reaction coordinate that induces energy shifts and couplings between various electronic states. Time-dependent wave packet calculations incorporating a simple dissipation mechanism indicate that the fast energy quenching results from a doorway state with a charge-transfer character that is only transiently populated. The identified relaxation mechanism corresponds to a possible exciton trap in molecular materials.

[1]  Zhijian Chen,et al.  Exciton delocalization and dynamics in helical π-stacks of self-assembled perylene bisimides , 2013 .

[2]  Bernd Engels,et al.  Comparison of the electronic structure of different perylene‐based dye‐aggregates , 2012, J. Comput. Chem..

[3]  Chen Li,et al.  Perylene Imides for Organic Photovoltaics: Yesterday, Today, and Tomorrow , 2012, Advanced materials.

[4]  A. Eisfeld,et al.  Intermolecular torsional motion of a π-aggregated dimer probed by two-dimensional electronic spectroscopy. , 2012, The Journal of chemical physics.

[5]  Andreas Dreuw,et al.  Assessment of TD‐DFT‐ and TD‐HF‐based approaches for the prediction of exciton coupling parameters, potential energy curves, and electronic characters of electronically excited aggregates , 2011, J. Comput. Chem..

[6]  F. Würthner,et al.  One-dimensional exciton diffusion in perylene bisimide aggregates. , 2011, The journal of physical chemistry. A.

[7]  V. May,et al.  Charge and Energy Transfer Dynamics in Molecular Systems: MAY:CHARGE TRANSFER 3ED O-BK , 2011 .

[8]  A. Roitberg,et al.  Nonadiabatic excited-state molecular dynamics modeling of photoinduced dynamics in conjugated molecules. , 2011, The journal of physical chemistry. B.

[9]  Richard H. Friend,et al.  Perylene Tetracarboxydiimide as an Electron Acceptor in Organic Solar Cells: A Study of Charge Generation and Recombination , 2009 .

[10]  M. Wasielewski,et al.  Self-assembly strategies for integrating light harvesting and charge separation in artificial photosynthetic systems. , 2009, Accounts of chemical research.

[11]  Bernd Engels,et al.  Exciton trapping in pi-conjugated materials: a quantum-chemistry-based protocol applied to perylene bisimide dye aggregates. , 2008, Journal of the American Chemical Society.

[12]  Arnim Hellweg,et al.  Benchmarking the performance of spin-component scaled CC2 in ground and electronically excited states. , 2008, Physical chemistry chemical physics : PCCP.

[13]  David Beljonne,et al.  Trap Limited Exciton Transport in Conjugated Polymers , 2008 .

[14]  P. Marquetand,et al.  Photoluminescence and Conductivity of Self-Assembled π–π Stacks of Perylene Bisimide Dyes , 2007 .

[15]  Philipp Marquetand,et al.  On the geometry dependence of molecular dimer spectra with an application to aggregates of perylene bisimide , 2006 .

[16]  Zhijian Chen,et al.  One-dimensional luminescent nanoaggregates of perylene bisimides. , 2006, Chemical communications.

[17]  David Beljonne,et al.  Charge-transfer and energy-transfer processes in pi-conjugated oligomers and polymers: a molecular picture. , 2004, Chemical reviews.

[18]  M. Head‐Gordon,et al.  Failure of time-dependent density functional theory for long-range charge-transfer excited states: the zincbacteriochlorin-bacteriochlorin and bacteriochlorophyll-spheroidene complexes. , 2004, Journal of the American Chemical Society.

[19]  S. Grimme.  Improved second-order Møller–Plesset perturbation theory by separate scaling of parallel- and antiparallel-spin pair correlation energies , 2003 .

[20]  Christof Hättig,et al.  Transition moments and excited-state first-order properties in the coupled-cluster model CC2 using the resolution-of-the-identity approximation , 2002 .

[21]  M. Wasielewski,et al.  Excited-state symmetry breaking in cofacial and linear dimers of a green perylenediimide chlorophyll analogue leading to ultrafast charge separation. , 2002, Journal of the American Chemical Society.

[22]  Andr'e Nauts,et al.  Exact numerical computation of a kinetic energy operator in curvilinear coordinates , 2002 .

[23]  Christof Hättig,et al.  CC2 excitation energy calculations on large molecules using the resolution of the identity approximation , 2000 .

[24]  Holger Patzelt,et al.  RI-MP2: optimized auxiliary basis sets and demonstration of efficiency , 1998 .

[25]  Stephen R. Forrest,et al.  Ultrathin Organic Films Grown by Organic Molecular Beam Deposition and Related Techniques. , 1997, Chemical reviews.

[26]  Ove Christiansen,et al.  Response functions in the CC3 iterative triple excitation model , 1995 .

[27]  Hans W. Horn,et al.  Fully optimized contracted Gaussian basis sets for atoms Li to Kr , 1992 .

[28]  S. Shaik,et al.  Symmetry Breaking and Non‐Born‐Oppenheimer Effects in Radical Cations , 1983 .

[29]  M. Feit,et al.  Solution of the Schrödinger equation by a spectral method , 1982 .