Singlet excited state surface

A similar supramolecular approach, in which both n-n stacking stacking of pyrene on the SWNT surface and alkyl ammonium-crown ether interactions were used in the self-assembly process of a fullerene derivative with SWNTs, was recently reported (Scheme 9.22).72 The nanohybrid integrity was probed with various spectroscopic techniques, , and electrochemical measurements. Nanosecond transient absorption studies confirmed electron transfer as the quenching mechanism of the singlet excited state of C60 in the nanohybrid resulting in the formation of SWNT"1"/ Pyr-NH3 + /crown- charge-separated state. 

Photo-oxidation of LCV by the Pyrene-Bonded Film. The surface properties and structure of these systems should be related to the sensitizer efficiency of pyrenyl groups. Pyrene is a good sensitizer for the oxidative color formation of LCV. The singlet excited state of Py acts as an electron acceptor bringing about one electron oxidation of LCV+. The unit processes are considered as... 

Transient absorption experiments have shown that all of the major DNA and RNA nucleosides have fluorescence lifetimes of less than one picosecond [2—4], and that covalently modified bases [5], and even individual tautomers [6], differ dramatically in their excited-state dynamics. Femtosecond fluorescence up-conversion studies have also shown that the lowest singlet excited states of monomeric bases, nucleosides, and nucleotides decay by ultrafast internal conversion [7-9]. As discussed elsewhere [2], solvent effects on the fluorescence lifetimes are quite modest, and no evidence has been found to date to support excited-state proton transfer as a decay mechanism. These observations have focused attention on the possibility of internal conversion via one or more conical intersections. Recently, computational studies have succeeded in locating conical intersections on the excited state potential energy surfaces of several isolated nucleobases [10-12]. 

The rate for moving from one minimum to another on the surface of the first singlet excited state S, is then in competition with radiative rates if the barrier between two minima is sufficiently small. Consequently, for the study of dual fluorescence, two aspects should be investigated (1) the possibility of existence of two minima on the S, energy surface with... 

Therefore, inhibiting cluster formation is a possible way to avoid the problem of suppressed electron transfer. There are several methods to reduce cluster formation, e.g., by capping the surface with surfactants like lauryl-sulfate or cetyltrimethylammonium chloride, or by incorporating the fullerene derivatives into the cavity of -y-cyclodextrines [182-185,187], Transient absorption spectroscopy show that excitation to the singlet-excited state and intersystem crossing to the triplet are not effected by surfacting or incorporating fullerene derivatives... 

Dyes such as erythrosin B [172], eosin [173-177], rose bengal [178,179], rhodamines [180-185], cresyl violet [186-191], thionine [192], chlorophyll a and b [193-198], chlorophyllin [197,199], anthracene-9-carboxylate [200,201], perylene [202,203] 8-hydroxyquinoline [204], porphyrins [205], phthalocyanines [206,207], transition metal cyanides [208,209], Ru(bpy)32+ and its analogs [83,170,210-218], cyanines [169,219-226], squaraines [55,227-230], and phe-nylfluorone [231] which have high extinction coefficients in the visible, are often employed to extend the photoresponse of the semiconductor in photoelectro-chemical systems. Visible light sensitization of platinized Ti02 photocatalyst by surface-coated polymers derivatized with ruthenium tris(bipyridyl) complex has also been attempted [232,233]. Because the singlet excited state of these dyes is short lived it becomes essential to adsorb them on the semiconductor surface with... 

In the present chapter, we will focus on the simulation of the dynamics of photoexcited nucleobases, in particular on the investigation of radiationless decay dynamics and the determination of associated characteristic time constants. We use a nonadiabatic extension of ab initio molecular dynamics (AIMD) [15, 18, 21, 22] which is formulated entirely within the framework of density functional theory. This approach couples the restricted open-shell Kohn-Sham (ROKS) [26-28] first singlet excited state, Su to the Kohn-Sham ground state, S0, by means of the surface hopping method [15, 18, 94-97], The current implementation employs a plane-wave basis set in combination with periodic boundary conditions and is therefore ideally suited to condensed phase applications. Hence, in addition to gas phase reference simulations, we will also present nonadiabatic AIMD (na-AIMD) simulations of nucleobases and base pairs in aqueous solution. 

Figure 13-8. Relevant schematic potential energy curves for the near UV photophysics of the most stable tautomers of guanine. The region of the first singlet tht excited state surface accessible by Franck-Condon excitation is indicated in bold. Excited state internal conversion through a conical intersection (Cl) with S0 is illustrated by curved arrows. Vertical arrows indicate fluorescence emission. The eventual role of excited nir singlet states cannot be ruled out, especially at high energy excess in the excited state (see text)...

The photoisomerization of all types of azobenzenes is a very fast reaction on either the singlet or triplet excited-state surfaces according to the preparation of the excited state, with nearly no intersystem crossing. Bottleneck states have lifetimes on the order of 10 ps. The molecules either isomerize or return to their respective ground states with high efficiency. So photoisomerization is the predominant reactive channel, and the azobenKnes are photochemically stable. Only aminoazobenzene-type molecules and pseudo-stilbenes have small quantum yields of photodegradation. 

A detailed kinetic study (121) of the 7,7 -polymethylenedioxy-coumarins indicated that the reaction occurs partially from the singlet excited state manifold and partially from direct excitation of favorable ground state conformation. The latter are extremely important in the total reaction since they collapse to a product with high quantum yield while the reaction from singlet species is much less efficient. The total reaction scheme is presented in Scheme II. The lifetime of the different excited states involved could be estimated and a correlation with recently proposed models of energy surface crossings could be made (122-124). 

Buenker, R. J., Bonacic Koutecky, V., Pogliani, L., Potential energy and Dipole moment Surfaces for Simultaneous Torsion and Pyramidalization of Ethylene in Its Lowest lying Singlet Excited States A Cl Study of the Sudden Polarization Effect, J. Chem. Phys. 1980,73, 1836 1849. 

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