Vibronic Coupling in J-Aggregates and Beyond: A Direct Means of Determining the Exciton Coherence Length from the Photoluminescence Spectrum

被引:180
作者
Spano, Frank C. [1 ]
Yamagata, Hajime [1 ]
机构
[1] Temple Univ, Dept Chem, Philadelphia, PA 19122 USA
基金
美国国家科学基金会;
关键词
PHOTOSYNTHETIC ANTENNA COMPLEXES; PUMP-PROBE SPECTROSCOPY; TEMPERATURE-DEPENDENCE; SUPERRADIANT EMISSION; DELOCALIZATION LENGTH; FRENKEL EXCITONS; OPTICAL-SPECTRA; FLUORESCENCE; LIGHT; DYNAMICS;
D O I
10.1021/jp104752k
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Exciton coherence in a J-aggregate with exciton-phonon coupling involving a single intramolecular vibration is studied. For linear aggregates with no disorder and periodic boundary conditions, the 0-0 to 0-1 line strength ratio, S-R, corresponding to the low-temperature photoluminescence spectrum is rigorously equal to N/lambda(2), where N is the number of chromophores comprising the aggregate and lambda(2) is the Huang-Rhys factor of the coupled vibrational mode. The result is independent of exciton bandwidth and therefore remains exact from the weak to strong exciton-phonon coupling regimes. The simple relation between S-R and N also holds for more complex morphologies, as long as the transition from the lowest exciton state to the vibrationless ground state is symmetry-allowed. For example, in herringbone aggregates with monoclinic unit cells, the line strength ratio, defined as S-R equivalent to I-b(0-0)/I-b(0-1) (where I-b(0-0) and I-b(0-1) correspond to the b-polarized 0-0 and 0-1 line strengths, respectively) is rigorously equal to N/lambda(2). In the presence of disorder and for T > 0 K, lambda S-2(R) is closely approximated by the exciton coherence number N-coh, thereby providing a simple and direct way of extracting N-coh from the photoluminescence spectrum. Increasing temperature in linear J-aggregates (and herringbone aggregates) generally leads to a demise in S-R and therefore also the exciton coherence size. When no disorder is present, and under the fast scattering and thermodynamic limits, S-R is equal to N-T/lambda(2), where the thermal coherence size is given by N-T = 1 + [4 pi omega(c)/k(b)T](d/2) for an aggregate of dimension d, where omega(c) is the exciton band curvature at k = 0.
引用
收藏
页码:5133 / 5143
页数:11
相关论文
共 53 条
[1]   Experimental and theoretical study of temperature dependent exciton delocalization and relaxation in anthracene thin films [J].
Ahn, Tai-Sang ;
Mueller, Astrid M. ;
Al-Kaysi, Rabih O. ;
Spano, Frank C. ;
Norton, Joseph E. ;
Beljonne, David ;
Bredas, Jean-Luc ;
Bardeen, Christopher J. .
JOURNAL OF CHEMICAL PHYSICS, 2008, 128 (05)
[2]  
Bakalis LD, 1999, J PHYS CHEM B, V103, P6620, DOI 10.1021/jp990354gCCC:$18.00
[3]   Temperature dependent fluorescence in disordered Frenkel chains: Interplay of equilibration and local band-edge level structure [J].
Bednarz, M ;
Malyshev, VA ;
Knoester, J .
PHYSICAL REVIEW LETTERS, 2003, 91 (21)
[4]   Low-temperature dynamics of weakly localized Frenkel excitons in disordered linear chains [J].
Bednarz, M ;
Malyshev, VA ;
Knoester, J .
JOURNAL OF CHEMICAL PHYSICS, 2004, 120 (08) :3827-3840
[5]   Intraband relaxation and temperature dependence of the fluorescence decay time of one-dimensional Frenkel excitons: The Pauli master equation approach [J].
Bednarz, M ;
Malyshev, VA ;
Knoester, J .
JOURNAL OF CHEMICAL PHYSICS, 2002, 117 (13) :6200-6213
[6]   Fluorescence and photobleaching dynamics of single light-harvesting complexes [J].
Bopp, MA ;
Jia, YW ;
Li, LQ ;
Cogdell, RJ ;
Hochstrasser, RM .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1997, 94 (20) :10630-10635
[7]   Effect of interchain interactions on the absorption and emission of poly(3-hexylthiophene) -: art. no. 064203 [J].
Brown, PJ ;
Thomas, DS ;
Köhler, A ;
Wilson, JS ;
Kim, JS ;
Ramsdale, CM ;
Sirringhaus, H ;
Friend, RH .
PHYSICAL REVIEW B, 2003, 67 (06)
[8]   Polarized superradiance from delocalized exciton transitions in tetracene single crystals [J].
Camposeo, A. ;
Polo, M. ;
Tavazzi, S. ;
Silvestri, L. ;
Spearman, P. ;
Cingolani, R. ;
Pisignano, D. .
PHYSICAL REVIEW B, 2010, 81 (03)
[9]   Role of intermolecular coupling in the photophysics of disordered organic semiconductors: Aggregate emission in regioregular polythiophene [J].
Clark, Jenny ;
Silva, Carlos ;
Friend, Richard H. ;
Spano, Frank C. .
PHYSICAL REVIEW LETTERS, 2007, 98 (20)
[10]   Exciton delocalization in the B850 light-harvesting complex:: Comparison of different measures [J].
Dahlbom, M ;
Pullerits, T ;
Mukamel, S ;
Sandström, V .
JOURNAL OF PHYSICAL CHEMISTRY B, 2001, 105 (23) :5515-5524