%0 Journal Article %1 Hernando2003 %A Hernando, J %A van der Schaaf, M %A van Dijk, EMHP %A Sauer, M %A Garcia-Parajo, MF %A van Hulst, NF %C 1155 16TH ST, NW, WASHINGTON, DC 20036 USA %D 2003 %I AMER CHEMICAL SOC %J JOURNAL OF PHYSICAL CHEMISTRY A %K sauer %N 1 %P 43-52 %T Excitonic behavior of rhodamine dimers: A single-molecule study %U http://dx.doi.org/10.1021/jp0218995 %V 107 %X The optical behavior of a dimer of tetramethylrhodamine-5-isothiocyanate has been investigated by means of single-molecule measurements. Bulk absorption and fluorescence spectra show the existence of two populations of the dimer molecule that exhibit distinct excitonic interactions (strong and weak coupling). Fluorescence confocal scanning microscopy has been employed to analyze the behavior of the weakly coupled dimers at the single-molecule level. Stepwise photodamage and collective on/off behavior have been observed in real-time fluorescence trajectories of the dimer. By polarization-sensitive detection, we distinguished between two conformationally different subpopulations within the weakly interacting dimers. Correlation between the fluorescence intensity and fluorescence lifetime of the dimer recorded in time has revealed the competition between photobleaching and trap formation as photodamaging processes of the chromophores in the dimer. The results obtained demonstrate the capability of single-molecule techniques to provide detailed insight into the exciton dynamics in multichromophoric systems, which is a key point in understanding the behavior of relevant natural aggregates and, eventually, in allowing for a rational design of molecular photonic devices.

@article{Hernando2003, abstract = {The optical behavior of a dimer of tetramethylrhodamine-5-isothiocyanate has been investigated by means of single-molecule measurements. Bulk absorption and fluorescence spectra show the existence of two populations of the dimer molecule that exhibit distinct excitonic interactions (strong and weak coupling). Fluorescence confocal scanning microscopy has been employed to analyze the behavior of the weakly coupled dimers at the single-molecule level. Stepwise photodamage and collective on/off behavior have been observed in real-time fluorescence trajectories of the dimer. By polarization-sensitive detection, we distinguished between two conformationally different subpopulations within the weakly interacting dimers. Correlation between the fluorescence intensity and fluorescence lifetime of the dimer recorded in time has revealed the competition between photobleaching and trap formation as photodamaging processes of the chromophores in the dimer. The results obtained demonstrate the capability of single-molecule techniques to provide detailed insight into the exciton dynamics in multichromophoric systems, which is a key point in understanding the behavior of relevant natural aggregates and, eventually, in allowing for a rational design of molecular photonic devices.}, added-at = {2011-03-01T10:57:13.000+0100}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, affiliation = {Hernando, J (Reprint Author), Univ Twente, Appl Opt Grp, Dept Appl Phys, POB 217, NL-7500 AE Enschede, Netherlands. Univ Twente, Appl Opt Grp, Dept Appl Phys, NL-7500 AE Enschede, Netherlands. Univ Twente, MESA, Res Inst, NL-7500 AE Enschede, Netherlands. Univ Heidelberg, Inst Chem Phys, D-69120 Heidelberg, Germany.}, author = {Hernando, J and van der Schaaf, M and van Dijk, EMHP and Sauer, M and Garcia-Parajo, MF and van Hulst, NF}, biburl = {https://www.bibsonomy.org/bibtex/28feab2849b92af850edc80e036aa9620/reichert}, cited-references = {BOPP MA, 1997, P NATL ACAD SCI USA, V94, P10630. BOPP MA, 1999, P NATL ACAD SCI USA, V96, P11271. CHRIST T, 2002, J LUMIN, V98, P23. COTLET M, 2001, CHEM PHYS LETT, V336, P415. DAVYDOV AS, 1982, THEORY MOL EXCITON. DELMONTE F, 1999, J PHYS CHEM B, V103, P8080. DENIZ AA, 1999, P NATL ACAD SCI USA, V96, P3670. DEXTER DL, 1953, J CHEM PHYS, V21, P836. FIRSCH MJ, 1998, GAUSSIAN 98 REVISION. FORSTER T, 1965, MODERN QUANTUM CHEM. GARCIAPARAJO MF, 2001, P NATL ACAD SCI USA, V98, P14392. GENSCH T, 2001, SINGLE MOL, V1, P35. GRONHEID R, 2001, J AM CHEM SOC, V124, P2418. HA T, 1997, CHEM PHYS LETT, V271, P1. HIGGINS DA, 1996, J PHYS CHEM-US, V100, P1174. HOFKENS J, 2000, J AM CHEM SOC, V122, P9278. HOFKENS J, 2001, SPECTROCHIM ACTA A, V57, P2093. HSU CP, 2001, J PHYS CHEM B, V105, P11016. HU DH, 1999, J AM CHEM SOC, V121, P6936. HUSER T, 2000, P NATL ACAD SCI USA, V97, P11187. JELEZKO F, 2000, J PHYS CHEM B, V104, P8093. KASHA M, 1965, PURE APPL CHEM, V11, P371. KEMNITZ K, 1991, J PHYS CHEM-US, V95, P6095. KOHN F, 2000, CHEM PHYS LETT, V321, P373. LIANG KN, 1997, J AM CHEM SOC, V119, P830. LOUNIS B, 2001, J PHYS CHEM B, V105, P5048. LU HP, 1997, NATURE, V385, P143. LU LD, 1999, J AM CHEM SOC, V121, P8146. MOERNER WE, 1999, SCIENCE, V283, P1670. SCHLEGEL G, 2002, PHYS REV LETT, V88, ARTN 137401. TIETZ C, 1999, J PHYS CHEM B, V103, P6328. TIETZ C, 2001, BIOPHYS J, V81, P556. VALLEE R, 2001, CHEM PHYS LETT, V348, P161. VANDENBOUT DA, 1997, SCIENCE, V277, P1071. VANOIJEN AM, 1998, J PHYS CHEM B, V102, P9363. VANOIJEN AM, 1999, SCIENCE, V285, P400. VEERMAN JA, 1999, PHYS REV LETT, V83, P2155. VOSCH T, 2001, ANGEW CHEM INT EDIT, V40, P4643. WEISS S, 1999, SCIENCE, V283, P1676. WU M, 1996, J PHYS CHEM-US, V100, P17406. YING LM, 1998, J PHYS CHEM B, V102, P10399. YIP WT, 1998, J PHYS CHEM A, V102, P7564. YU J, 2000, SCIENCE, V289, P1327.}, doc-delivery-number = {632ZL}, groups = {public}, interhash = {06c321b13661ffa1b0c85fd5f3f165e5}, intrahash = {8feab2849b92af850edc80e036aa9620}, issn = {1089-5639}, journal = {JOURNAL OF PHYSICAL CHEMISTRY A}, journal-iso = {J. Phys. Chem. A}, keywords = {sauer}, keywords-plus = {LIGHT-HARVESTING COMPLEXES; PIGMENT-PROTEIN COMPLEXES; RED FLUORESCENT PROTEIN; ENERGY-TRANSFER; ROOM-TEMPERATURE; SPECTROSCOPY; DYNAMICS; PHOTOCHEMISTRY; PHOTOPHYSICS; DEPENDENCE}, language = {English}, month = {JAN 9}, number = 1, number-of-cited-references = {43}, pages = {43-52}, publisher = {AMER CHEMICAL SOC}, subject-category = {Chemistry, Physical; Physics, Atomic, Molecular \& Chemical}, times-cited = {47}, timestamp = {2011-03-09T14:16:48.000+0100}, title = {Excitonic behavior of rhodamine dimers: A single-molecule study}, type = {Article}, unique-id = {ISI:000180254700007}, url = {http://dx.doi.org/10.1021/jp0218995}, username = {reichert}, volume = 107, year = 2003 }