Temperature dependence of the lowest excited singlet‐state lifetime of all‐trans‐β‐carotene and fully deuterated all‐trans‐β‐carotene

A 4 ps, 450 nm laser pulse was used to electronically excite all‐trans‐β‐carotene and all‐trans‐β‐carotene‐d56 in 3‐methylpentane. The transient absorption spectra of these molecules were measured as a function of temperature down to 20 K. In all cases the 400–500 nm electronic absorption band of each carotene bleaches and a new absorption band near 560 nm appears immediately upon excitation. These bands recover with single exponential kinetics: τ=8.1±0.5 ps for all‐trans‐β‐carotene, and τ=10.5±0.6 ps for all‐trans‐β‐carotene‐d56 at 294 K. These recovery times increase by about a factor of 2 in glassy 3‐methylpentane, and are nearly independent of temperature from 100 to 20 K. The weak dependencies of the lowest excited single‐state lifetime of all‐trans‐β‐carotene on deuteration and temperature are discussed in terms of nonradiative decay mechanisms within carotenoids.

[1]  S. L. Bondarev,et al.  S2 → S0 fluorescence and transient Sn ← S1 absorption of all-rans-β-carotene in solid and liquid solutions , 1989 .

[2]  H. Hashimoto,et al.  The CC stretching Raman lines of [β-carotene isomers in the S1 state as detected by pump-probe resonance Raman spectroscopy , 1989 .

[3]  Curtis L. Westerfield,et al.  The 2 1Ag state in the linear polyene 2,4,6,8,10,12,14,16‐octadecaoctaene , 1988 .

[4]  F. Zerbetto,et al.  Theoretical study of the force fields of the three lowest singlet electronic states of linear polyenes , 1988 .

[5]  H. Villar,et al.  Structure, vibrational spectra, and IR intensities of polyenes from ab initio SCF calculations , 1988 .

[6]  F. Zerbetto,et al.  Correlation between the frequency of the Franck-Condon active CC ag stretch vibration and the excitation energy of the 1Bu electronic state in polyenes , 1987 .

[7]  D. S. Smith,et al.  Vibronic coupling in polyenes: High resolution optical spectroscopy of all‐trans‐2,4,6,8,10,12,14‐hexadecaheptaene , 1987 .

[8]  G. Marconi,et al.  Vibronic coupling in polyenes and their derivatives. Interpretation of the absorption and emission spectra of a derivative of dodecahexaene , 1987 .

[9]  L. Brus,et al.  Saturation and nonlinear electromagnetic field effects in the picosecond resonance Raman spectra of β‐carotene , 1987 .

[10]  F. Zerbetto,et al.  Vibronic coupling in polyenes: The frequency increase of the active CC ag stretching mode in the absorption spectra , 1986 .

[11]  M. Wasielewski,et al.  Ultrafast carotenoid to pheophorbide energy transfer in a biomimetic model for antenna function in photosynthesis , 1986, Nature.

[12]  Michael R. Wasielewski,et al.  Direct measurement of the lowest excited singlet state lifetime of all-trans-β-carotene and related carotenoids , 1986 .

[13]  D. Siefermann-Harms.  Carotenoids in photosynthesis. I: Location in photosynthetic membranes and light-harvesting function , 1985 .

[14]  J. Brédas,et al.  Long polyene and polydiacetylene oligomers: Pariser–Parr–Pople investigation of the geometric and electronic structures in the first 1Bu excited state , 1985 .

[15]  Eamonn F. Healy,et al.  Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model , 1985 .

[16]  G. Mourou,et al.  Generation of pulses shorter than 70 fs with a synchronously-pumped CW dye laser , 1982 .

[17]  M. F. Granville,et al.  Franck–Condon analysis of the 1 1Ag→1 1Bu absorption in linear polyenes with two through six double bonds , 1981 .

[18]  M. F. Granville,et al.  Absorption and emission of 2,12‐dimethyltridecahexaene , 1981 .

[19]  Gary R. Holtom,et al.  High‐resolution one and two photon excitation spectra of trans, trans‐1,3,5,7‐octatetraene , 1980 .

[20]  K. Naqvi,et al.  THE MECHANISM OF SINGLET‐SINGLET EXCITATION ENERGY TRANSFER FROM CAROTENOIDS TO CHLOROPHYLL , 1980 .

[21]  G. E. Leroi,et al.  ON THE ROLE OF FORBIDDEN LOW‐LYING EXCITED STATES OF LIGHT‐HARVESTING CAROTENOIDS IN ENERGY TRANSFER IN PHOTOSYNTHESIS * , 1979 .

[22]  G. E. Leroi,et al.  The Raman excitation profile spectrum of β‐carotene in the preresonance region: Evidence for a low‐lying singlet state , 1977 .

[23]  R. L. Christensen,et al.  High-resolution optical spectroscopy of polyenes related to the visual chromophore , 1976 .

[24]  A. Grinvald.  The use of standards in the analysis of fluorescence decay data. , 1976, Analytical biochemistry.

[25]  Klaus Schulten,et al.  Correlation effects in the spectra of polyenes , 1976 .

[26]  R. L. Christensen,et al.  Vibronic coupling in polyenes: High resolution optical spectroscopy of 2,10‐dimethylundecapentaene , 1975 .

[27]  T. Moore,et al.  ON THE PHOTORECEPTOR PIGMENT FOR PHOTOTROPISM AND PHOTOTAXIS: IS A CAROTENOID THE MOST LIKELY CANDIDATE? * , 1974, Photochemistry and photobiology.

[28]  J. Willard,et al.  Viscosities of some organic glasses used as trapping matrixes , 1968 .

[29]  S. J. Strickler,et al.  Relationship between Absorption Intensity and Fluorescence Lifetime of Molecules , 1962 .

[30]  J. Katz,et al.  CHLOROPLAST PIGMENTS AND PHOTOSYNTHESIS IN DEUTERATED GREEN ALGAE * , 1960 .