STARK SPECTROSCOPY: Applications in Chemistry, Biology, and Materials Science

Bublitz, Gerold U.; Boxer, Steven G.

doi:10.1146/annurev.physchem.48.1.213

Cited by 584 publications

(799 citation statements)

References 86 publications

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“…This emission, denoted by EX ECZ-DMTP (38), noticeably increases with application of H even in the absence of F (see Figure 4b), which is exceptional, as will be mentioned later. …”

Section: Magnetic Field Effects On E-pl Of D-a Pairs In Type (I)mentioning

confidence: 57%

“…In fact, the total intensity of the exciplex fluorescence of i.e., another exciplex fluorescence between ECZ and DMTP, which shows the magnetic field effects not only on I PL but also on I PL , was observed. The monotonic H dependence of I PL (H) of EX ECZ-DMTP (38) reminds us the g mechanism for the magnetic field effects, where the difference of the g factor between both radicals plays an important role in magnetic field effects on ISC between the singlet and triplet states of RIPs [20]. Only when the ECZ concentration is high, EX ECZ-DMTP (38) was observed, suggesting that this is a kind of exciplex composed of DMTP and an aggregate of ECZ, but the exact origin of EX ECZ-DMTP (38) is not known.…”

Section: Discussionmentioning

confidence: 98%

“…In the former case, however, the synergy effect of F and H was observed even when the concentrations of ECZ and DCB were replaced by each other, as mentioned below. In the pair of ECZ and DMTP, further, two kinds of exciplex fluorescence, i.e., EX ECZ-DMTP (38) and EX ECZ-DMTP (45), exist in a PMMA film.…”

Section: Magnetic Field Effects On E-pl Of D-a Pairs In Type (Ii)mentioning

confidence: 99%

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Magnetic field effects on electro-photoluminescence of photoinduced electron transfer systems in a polymer film

Awasthi

Ohta

2011

Journal of Photochemistry and Photobiology A: Chemistry

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Magnetic field effects on photoluminescence (PL) in the presence of external electric fields have been examined for a variety of electron donor and acceptor pairs, either linked with methylene chain or randomly distributed in polymethyl methacrylate (PMMA) films, which show intermolecular photoinduced electron transfer (PIET). Application of electric fields changes the energy separation among different electronic states, because the electric dipole moment at the state under consideration is usually different from the others. The energy levels within the same spin multiplicity are also shifted or splitted by application of magnetic field. Then, simultaneous application of electric field and magnetic field induces interesting effects on PL which cannot be observed when only electric field or magnetic field is applied to molecules. In this article, experimental results of the magnetic field effect of the electric field effect both on LE fluorescence and on exciplex fluorescence resulting from PIET are presented, and the mechanism of the synergy effects of the electric and magnetic fields on PL are discussed. The hyperfine interaction of the various radical-ion pairs produced by PIET has been also determined on the basis of the synergy effects on PL, and the results are compared with the calculated values.

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“…This emission, denoted by EX ECZ-DMTP (38), noticeably increases with application of H even in the absence of F (see Figure 4b), which is exceptional, as will be mentioned later. …”

Section: Magnetic Field Effects On E-pl Of D-a Pairs In Type (I)mentioning

confidence: 57%

Section: Discussionmentioning

confidence: 98%

Section: Magnetic Field Effects On E-pl Of D-a Pairs In Type (Ii)mentioning

confidence: 99%

See 1 more Smart Citation

Magnetic field effects on electro-photoluminescence of photoinduced electron transfer systems in a polymer film

Awasthi

Ohta

2011

Journal of Photochemistry and Photobiology A: Chemistry

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“…22,23 Site specific mutant Rb. sphaeroides strains (M)Y210F and (M)L214H (the mutant) were generously provided by Dr. C. Schenck.…”

Section: Experimental Methodsmentioning

confidence: 99%

Probing Excited-State Electron Transfer by Resonance Stark Spectroscopy. 2. Theory and Application

Zhou

Boxer

1998

J. Phys. Chem. B

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Higher order Stark spectroscopy has recently been introduced and applied to characterize the electrooptic properties of chromophores in bacterial photosynthetic reaction centers. 1 In the course of these studies, an unusually large and broad higher order Stark effect with a novel line shape was discovered in the region of the monomeric bacteriochlorophyll absorption band. The origin of this new feature has been explored by comparing results from reaction centers in which the chromophores are modified or the environment around the chromophores has an altered amino acid residue composition. Taken together, these results demonstrate that this unusual higher order Stark effect is related to both the monomeric bacteriochlorophyll and bacteriopheophytin on the electron-transfer pathway of the reaction center. The effects of mutations and the oxidation of the special pair on this signal specifically suggest the involvement of charge-separated species between these monomeric chromophores. In part 2 (following paper in this issue) we develop a general treatment of this phenomenon based on a charge resonance interaction between a strongly allowed transition and a charge-separated state. This leads to a variety of predicted higher order Stark line shapes which span the range observed in part 1 and from which we can obtain information on these potentially important, but heretofore experimentally inaccessible, charge-separated states.There has been extensive experimental and theoretical work directed toward a deeper understanding of the mechanism of the initial electron-transfer steps in photosynthesis. A schematic diagram of the chromophore arrangement derived from the X-ray structure 2,3 is shown in Figure 1. Two closely interacting bacteriochlorophylls (BChls) form the dimeric special pair P, which is the primary electron donor. There are two accessory BChls designated B, two bacteriopheophytins (BPhe) designated H, and two quinones (not shown). Despite the structural pseudo C 2 symmetry obvious from the structure, electron transfer occurs predominantly along the L-branch of monomeric chromophores, as illustrated with a quantum yield approaching unity. [4][5][6] This extremely efficient and unidirectional electron transfer has stimulated much experimental and theoretical interest. 7-10 The role of the accessory BChl on the functional side (B L ) in facilitating the electron-transfer reaction from 1 P to P + H L -is an unresolved problem. Two limiting mechanisms have emerged: a two-step mechanism in which electron transfer occurs sequentially from 1 P to form the intermediate state P + B Land subsequently P + H L -11,12 and a direct one-step electron transfer from 1 P to form P + H L -, where the P + B L -state serves as a virtual intermediate to enhance the electronic coupling between 1 P and P + H L -by superexchange. 10,13,14 In either case, the B L molecule plays a crucial role, whether as P + B L -or B L + H L -. 15,16 The role of B L no doubt is also critical to understanding the origin of unidirectional electron tra...

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“…2͑a͔͒. 7,8,12,13 QY does not depend on excitation energy irrespective of F. The change in polarizability and electric dipole moment, i.e., ⌬␣ and ͉⌬ ͉ between the emitting state and the ground state was evaluated to be 680Ϯ 15 Å 3 / f 2 and 8.0Ϯ 0.5 D / f, respectively. Here, f is the internal field factor.…”

mentioning

confidence: 99%

Photo- and field-induced charge-separation and phosphorescence quenching in organometallic complex Ir(ppy)3

Mehata

Ohta

2011

Applied Physics Letters

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Electric field effects on absorption and photoluminescence ͑PL͒ spectra of organometallic phosphorescent emitter Ir͑ppy͒ 3 , ͕tris͓2-phenylpyridinato-C 2 ,N͔ iridium ͑III͖͒ doped in a film of polymethyl methacrylate ͑PMMA͒ have been confirmed at temperatures in the range of 40-295 K. Field-induced quenching of PL observed for Ir͑ppy͒ 3 is attributed to the decrease both of emitting state population and of the lifetime of PL. The quenching is independent of excitation energy as well as temperature. Field-assisted charge separation or dissociation of electron-hole ͑e-h͒ pair produced by photoexcitation may decrease the population of the emitting state. The Stark shifts on absorption and PL spectra have also been analyzed.

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STARK SPECTROSCOPY: Applications in Chemistry, Biology, and Materials Science

Cited by 584 publications

References 86 publications

Magnetic field effects on electro-photoluminescence of photoinduced electron transfer systems in a polymer film

Magnetic field effects on electro-photoluminescence of photoinduced electron transfer systems in a polymer film

Probing Excited-State Electron Transfer by Resonance Stark Spectroscopy. 2. Theory and Application

Photo- and field-induced charge-separation and phosphorescence quenching in organometallic complex Ir(ppy)3

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