Terry L. Gustafson

Characterization of electronic structure and defect states of thin epitaxial BiFeO3 films by UV-visible absorption and cathodoluminescence spectroscopies

UV-visible absorption and cathodoluminescence spectra of phase-pure epitaxial BiFeO3 thin films grown on SrTiO3(001) substrates by ultrahigh vacuum sputtering reveal a bandgap of 2.69–2.73eV for highly strained ∼70nm thick BiFeO3 films. This bandgap value agrees with theoretical calculations and recent experimental results of epitaxial BiFeO3 films, demonstrating only minimal bandgap change with lattice distortion. Both absorption and cathodoluminescence spectra show defect transitions at 2.20 and 2.45eV, of which the latter can be attributed to defect states due to oxygen vacancies.

Blue electroluminescent devices based on soluble poly(p‐pyridine)

We have fabricated unilayer electroluminescent devices from soluble poly(p‐pyridine) (PPy). The solubility of PPy in weak acids allows direct spin casting of the polymer films. The electroluminescence spectrum peaks at 2.5 eV (497 nm) corresponding to white light weighted towards the blue end of the spectrum. The photoluminescence spectrum peaks at 2.35 eV (530 nm). The operating voltages of the devices ranged from 4 to 12 V with current densities of 6 to 8 mA/mm2. We compare our devices with similar blue emitting devices based on poly(p‐phenylene).

Picosecond transient Raman spectroscopy: The photoisomerization of trans‐stilbene

We measured picosecond transient resonance Raman spectra of t‐stilbene in hexane using a high repetition rate, amplified, synchronously pumped dye laser. We assign four vibrational frequencies to the olefinic moiety. Two of these frequencies, 1238 and 1565 cm−1, have broad, asymmetric bands. We attribute this band shape to a distribution of excited state molecular conformers having different single and double bond strengths.

Poly (p-pyridine) - and poly (p-pyridyl vinylene) -based polymers: their photophysics and application to SCALE devices

Abstract Photophysics and light-emitting device applications of poly ( p -pyridine) - and poly( p -pyridyl vinylene)-based polymers are presented. Extensive time-resolved (ps to ms) photoluminescence, stimulated emission and photoinduced absorption studies of solutions, powders and films demonstrate that the primary photoexcitation of these polymers is an intrachain singlet exciton. The presence of (n,π * ) states leads to enhanced intersystem crossing to triplet excitons for the powder form, while aggregate formation plays a key role in the films. Polarons are important at longer times. These polymers were used to fabricate ‘conventional’ polymer light-emitting diodes. In addition, these polymers were used to demonstrate a novel light-emitting structure, the symmetrically configured a.c. light-emitting (SCALE) device. These new devices have potential advantages in their use with high workfunction electrodes, such as gold, and also in their a.c. operation.

Electron delocalization in the S1 and T1 metal-to-ligand charge transfer states of trans-substituted metal quadruply bonded complexes

The singlet S1 and triplet T1 photoexcited states of the compounds containing MM quadruple bonds trans-M2(TiPB)2(O2CC6H4-4-CN)2, where TiPB = 2,4,6-triisopropylbenzoate and M = Mo (I) or M = W (I′), and trans-M2(O2CMe)2((N[i Pr ])2CC ≡ CC6H5)2, where M = Mo (II) and M = W (II′), have been investigated by a variety of spectroscopic techniques including femtosecond time-resolved infrared spectroscopy. The singlet states are shown to be delocalized metal-to-ligand charge transfer (MLCT) states for I and I′ but localized for II and II′ involving the cyanobenzoate or amidinate ligands, respectively. The triplet states are MoMoδδ* for both I and II but delocalized 3MLCT for I′ and localized 3MLCT for II′. These differences arise from consideration of the relative orbital energies of the M2δ or M2δ* and the ligand π∗ as well as the magnitudes of orbital overlap.

Functional asymmetry of photosystem II D1 and D2 peripheral chlorophyll mutants of Chlamydomonas reinhardtii.

The peripheral accessory chlorophylls (Chls) of the photosystem II (PSII) reaction center (RC) are coordinated by a pair of symmetry-related histidine residues (D1-H118 and D2-H117). These Chls participate in energy transfer from the proximal antennae complexes (CP43 and CP47) to the RC core chromophores. In addition, one or both of the peripheral Chls are redox-active and participate in a low-quantum-yield electron transfer cycle around PSII. We demonstrate that conservative mutations of the D2-H117 residue result in decreased Chl fluorescence quenching efficiency attributed to reduced accumulation of the peripheral accessory Chl cation, Chl\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \setlength{\oddsidemargin}{-69pt} \begin{document} \begin{equation*}{\mathrm{_{Z}^{+}}}\end{equation*}\end{document}. In contrast, identical symmetry-related mutations at residue D1-H118 had no effect on Chl fluorescence yield or quenching kinetics. Mutagenesis of the D2-H117 residue also altered the line width of the Chl\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \setlength{\oddsidemargin}{-69pt} \begin{document} \begin{equation*}{\mathrm{_{Z}^{+}}}\end{equation*}\end{document} EPR signal, but the line shape of the D1-H118Q mutant remained unchanged. The D1-H118 and D2-H117 mutations also altered energy transfer properties in PSII RCs. Unlike wild type or the D1-H118Q mutant, D2-H117N RCs exhibited a reduced CD doublet in the red region of Chl absorbance band, indicative of reduced energetic coupling between P680 and the peripheral accessory Chl. In addition, transient absorption measurements of D2-H117N RCs, excited on the blue side of the Chl absorbance band, exhibited a (≈400 fs) pheophytin QX band bleach lifetime component not seen in wild-type or D1-H118Q RCs. The origin of this component may be related to delayed fast-energy equilibration of the excited state between the core pigments of this mutant.

The remarkable influence of M2δ to thienyl π conjugation in oligothiophenes incorporating MM quadruple bonds

Oligothiophenes incorporating MM quadruple bonds have been prepared from the reactions between Mo2(TiPB)4 (TiPB = 2,4,6-triisopropyl benzoate) and 3′,4′-dihexyl-2,2′-:5′,2″-terthiophene-5,5″-dicarboxylic acid. The oligomers of empirical formula Mo2(TiPB)2(O2C(Th)-C4(n-hexyl)2S-(Th)CO2) are soluble in THF and form thin films with spin-coating (Th = thiophene). The reactions between Mo2(TiPB)4 and 2-thienylcarboxylic acid (Th-H), 2,2′-bithiophene-5-carboxylic acid (BTh-H), and (2,2′:5′,2″-terthiophene)-5-carboxylic acid (TTh-H) yield compounds of formula trans-Mo2(TiPB)2L2, where L = Th, BTh, and TTh (the corresponding thienylcarboxylate), and these compounds are considered as models for the aforementioned oligomers. In all cases, the thienyl groups are substituted or coupled at the 2,5 positions. Based on the x-ray analysis, the molecular structure of trans-Mo2(TiPB)2(BTh)2 reveals an extended Lπ-M2δ-Lπ conjugation. Calculations of the electronic structures on model compounds, in which the TiPB are substituted by formate ligands, reveal that the HOMO is mainly attributed to the M2δ orbital, which is stabilized by back-bonding to one of the thienylcarboxylate π* combinations, and the LUMO is an in-phase combination of the thienylcarboxylate π* orbitals. The compounds and the oligomers are intensely colored due to M2δ–thienyl carboxylate π* charge transfer transitions that fall in the visible region of the spectrum. For the molybdenum complexes and their oligomers, the photophysical properties have been studied by steady-state absorption spectroscopy and emission spectroscopy, together with time-resolved emission and transient absorption for the determination of relaxation dynamics. Remarkably, THF solutions the molybdenum complexes show room-temperature dual emission, fluorescence and phosphorescence, originating mainly from 1MLCT and 3MM(δδ*) states, respectively. With increasing number of thienyl rings from 1 to 3, the observed lifetimes of the 1MLCT state increase from 4 to 12 ps, while the phosphorescence lifetimes are ≈80 μs. The oligomers show similar photophysical properties as the corresponding monomers in THF but have notably longer-lived triplet states, ≈200 μs in thin films. These results, when compared with metallated oligothiophenes of the later transition elements, reveal that M2δ–thienyl π conjugation leads to a very small energy gap between the 1MLCT and 3MLCT states of <0.6 eV.

The dynamics of carbene solvation: an ultrafast study of p-biphenylyltrifluoromethylcarbene.

Ultrafast photolysis (lambda(ex) = 308 nm) of p-biphenylyltrifluoromethyl diazomethane (BpCN2CF3) releases singlet p-biphenylyltrifluoromethylcarbene (BpCCF3) which absorbs strongly at 385 nm in cyclohexane, immediately after the 300 fs laser pulse. The initial absorption maximum shifts to longer wavelengths in coordinating solvents (nitrile, ether, and alcohol). In low viscosity coordinating solvents, the initial absorption maximum further red shifts between 2 and 10 ps after the laser pulse. Similar effects are observed upon ultrafast photolysis of 2-fluorenyltrifluoromethyl diazomethane (FlCN2CF3) and therefore cannot be associated with torsional motion around the two phenyl rings of the biphenyl compound. Instead, the effect is attributed to the dynamics of solvation of the singlet carbene. The time constant of solvation in normal alcohols lengthens with solvent viscosity in a linear manner. Furthermore, the time constants of the red shift in methanol-O-d (16 ps), ethanol-O-d (26 ps), 2-propanol-OD (40 ps), and 2,2,2-trifluoroethanol-O-d (14 ps) are longer than those recorded in methanol (9.6 ps, KIE = 1.7), ethanol (14.3 ps, KIE = 1.8), 2-propanol (28 ps, KIE = 1.4), and 2,2,2-trifluoroethanol (4.4 ps, KIE = 3.2), which indicates that the solvent reorganization involves formation of hydrogen bonds. The kinetic data are consistent with motion of the solvent to achieve a specific interaction with the carbene, with the creation of a new hydrogen bond. The solvated carbene reacts with the solvent over tens, hundreds, and thousands of ps, depending upon the solvent.

The structure of electronic excited states in trans‐stilbene: Picosecond transient Stokes and anti‐Stokes Raman spectra

We measured picosecond transient Stokes and anti‐Stokes Raman spectra of S1 trans‐stilbene in hexane. We observed 18 vibrational modes in the Stokes spectra and two modes in the low wave number anti‐Stokes spectra. The band positions and band shapes of the transient Raman spectra suggest a distribution of molecular conformers in S1 having different single and double bond strengths. The band intensities suggest a redistribution of electron density in Sn that is concentrated in the olefinic region and in the ortho and meta region of the phenyl rings.

Study of concerted and sequential photochemical Wolff Rearrangement by femtosecond UV-vis and IR spectroscopy.

Photoinduced Wolff rearrangements were studied by femtosecond time-resolved UV-vis and IR transient absorption spectroscopy. For BpCN2COCH3 in acetonitrile the IR data indicate the presence of at least two mechanisms of ketene formation. The first process is fast proceeding in either 1BpCN2COCH3*, or in a hot carbene, or in both species, while the second is slow proceeding through the intermediacy of a relaxed carbene. The slow time constant of the ketene formation dynamics obtained by ultrafast IR (700 ps) spectroscopy agrees with the relaxed carbene decay of 800 +/- 100 ps obtained by UV-vis absorption spectroscopy.