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Michl, Josef

Publications and source records attributed to Michl, Josef.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

An MS-CASPT2 Calculation of the Excited Electronic States of an Axial Difluoroborondipyrromethene (BODIPY) Dimer

The previously reported (Duman et al., J. Org. Chem. 2012, 77, 4516) calculated state energies of monomeric difluoroborondipyrromethene (BODIPY) and its axial dimer would suggest that these dyes are promising candidates for singlet fission, and the dimer was computed to have an unusual low-lying doubly excited state. We find that these results were affected by the use of an imbalanced active space in multireference calculations and are not correct. Multistate complete-active-space second-order perturbation theory (MS-CASPT2/cc-pVDZ) calculations using an [8,8] (8 electrons in 8 orbitals) active space for the monomer and a [16,16] active space for the dimer reproduce quite well the observed excitation energies of the S 1 states of both, and yield T 1 excitation energies well in excess of half of the S 1 excitation energies. We conclude that neither BODIPY monomer nor its axial dimer would permit exothermic singlet fission and are not worthy of investigation as potentially useful candidates, and that the unusual low-energy doubly excited states of the dimer were artifacts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

EPR Spectroscopy of Radical Ions of a 2,3-Diamino-1,4-naphthoquinone Derivative

We report the electron paramagnetic resonance spectra of the radical cation and radical anion of 1,2,2,3-tetramethyl-2,3-dihydro-1H-naphtho[2,3-d]imidazole-4,9-dione (1) and its doubly 13 C labeled analogue 2, of interest for singlet fission. The hyperfine coupling constants are in excellent agreement with density functional theory calculations and establish the structures beyond doubt. Unlike the radical cation 1 •+ , the radical anion 1 •– and its parent 1 have pyramidalized nitrogen atoms and inequivalent methyl groups 15 and 16, in agreement with the calculations. The distinction is particularly clear with the labeled analogue 2 •– .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Structure of a monolayer of molecular rotors on aqueous subphase from grazing-incidence X-ray diffraction

In situ grazing-incidence X-ray scattering shows here that a monolayer of artificial rod-shaped dipolar molecular rotors produced on the surface of an aqueous subphase in a Langmuir trough has a structure conducive to a 2D ferroelectric phase. The axes of the rotors stand an average of 0.83 nm apart in a triangular grid, perpendicular to the surface within experimental error. They carry 2,3-dichlorophenylene rotators near rod centers, between two decks of interlocked triptycenes installed axially on the rotor axle. The analysis is based first on simultaneous fitting of observed Bragg rods and second on fitting the reflectivity curve with only three adjustable parameters and the calculated rotor electron density, which also revealed the presence of about seven molecules of water near each rotator. Dependent on preparation conditions, a minor and variable amount of a different crystal phase may also be present in the monolayer.

36 MATERIALS SCIENCE↗
DOE OSTI2017

p -Carborane Conjugation in Radical Anions of Cage–Cage and Cage–Phenyl Compounds

Optical electron transfer (intervalence) transitions in radical anions of p-carborane oligomers attest to delocalization of electrons between two p-carboranes cages or a p-carborane and a phenyl ring. Oligomers of the 12 vertex p-carborane (C 2 B 10 H 12 ) cage, [12], with up to 3 cages were synthesized, as well as p-carboranes with one or two trimethylsilylphenyl groups, [6], attached to the carbon termini. Pulse radiolysis in tetrahydrofuran produced radical anions, determined redox potentials by equilibria and measured their absorption spectra. Density functional theory computations provided critical insight into the optical electron transfer bands and electron delocalization. One case, [6–12–6], showed both Robin–Day class II and III transitions. The class III transition resulted from a fully delocalized excess electron across both benzene rings and the central p-carborane, with an electronic coupling H ab = 0.46 eV between the cage and either benzene. This unprecedented finding shows that p-carborane bridges are not simply electron withdrawing insulators. In other cases with more than ~1/2 of the excess electron localized on a [12], large cage distortions were triggered, producing a partially open cage with a nido-like structure. This resulted in class II transitions with similar Hab but massive reorganization energies. The computations also predicted delocalization in radical cations, but complexities in cation formation allowed only tentative experimental support of the predictions. Thus, the results with anions provide clear evidence for carborane conjugation that might be exploited in molecular wire materials, which are classically composed of all π-conjugated molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Singlet Fission and Excimer Formation in Disordered Solids of Alkyl-Substituted 1,3-Diphenylisobenzofurans

Here, we describe the preparation and excited state dynamics of three alkyl derivatives of 1,3-diphenylisobenzofuran (1) in both solutions and thin films. The substitutions are intended to disrupt the slip-stacked packing observed in crystals of 1 while maintaining the favorable energies of singlet and triplet for singlet fission (SF). All substitutions result in films that are largely amorphous as judged by the absence of strong X-ray diffraction peaks. The films of 1 carrying a methyl in the para position of one phenyl ring undergo SF relatively efficiently (≥75% triplet yield, Φ T ) but more slowly than thin films of 1. When the methyl is replaced with a t-butyl, kinetic competition in the excited state favors excimer formation rather than SF (Φ T = 55%). When t-Bu groups are placed in both meta positions of the phenyl substituent, SF is slowed further and Φ T = 35%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

1,3-Diphenylisobenzofuran: a Model Chromophore for Singlet Fission

In this review we first provide an introductory description of the singlet fission phenomenon and then describe the ground and electronically excited states of the parent 1,3-diphenylisobenzofuran chromophore (1) and about a dozen of its derivatives. A discussion of singlet fission in thin polycrystalline layers of these materials follows. The highest quantum yield of triplet formation by singlet fission, 200% at 80 K, is found in one of the two known crystal modification of the parent. In the other modification and in many derivatives, excimer formation competes successfully and triplet yields are low. A description of solution photophysics of covalent dimers is described in the next section. Triplet yields are very low, but interesting phenomena are uncovered. One is an observation of a separated-charges (charge-transfer) intermediate in highly polar solvents. The other is an observation of excitation isomerism in both singlet and triplet states, where in one isomer the excitation is delocalized over both halves of the covalent dimer, whereas in the other it is localized on one of the halves. In the last section we present the operation of a simple device illustrating the use of triplets generated by singlet fission for charge separation.

1,3-Diphenylisobenzofuran↗
DOE OSTI2017

1,3-Diphenylisobenzofuran: a Model Chromophore for Singlet Fission

In this review we first provide an introductory description of the singlet fission phenomenon and then describe the ground and electronically excited states of the parent 1,3-diphenylisobenzofuran chromophore (1) and about a dozen of its derivatives. A discussion of singlet fission in thin polycrystalline layers of these materials follows. The highest quantum yield of triplet formation by singlet fission, 200% at 80 K, is found in one of the two known crystal modification of the parent. In the other modification and in many derivatives, excimer formation competes successfully and triplet yields are low. A description of solution photophysics of covalent dimers is described in the next section. Triplet yields are very low, but interesting phenomena are uncovered. One is an observation of a separated-charges (charge-transfer) intermediate in highly polar solvents. The other is an observation of excitation isomerism in both singlet and triplet states, where in one isomer the excitation is delocalized over both halves of the covalent dimer, whereas in the other it is localized on one of the halves. Finally, in the last section we present the operation of a simple device illustrating the use of triplets generated by singlet fission for charge separation.

1,3-diphenylisobenzofuran↗
DOE OSTI2017

Singlet Fission: Optimization of Chromophore Dimer Geometry

After a brief review of electronic aspects of singlet fission, we describe a systematic simplification of the frontier orbital (HOMO/LUMO) model of singlet fission and Davydov splitting in a pair of rigid molecules. In both instances, the model includes electron configurations representing local singlet excitation on either chromophore, charge transfer in either direction, and triplet excitation in both chromophores (biexciton). The resulting equations are simple enough to permit complete searches for local extrema of the square of the electronic matrix element and to evaluate the effect of intermolecular interactions on the exoergicity of singlet fission and on the biexciton binding energy in the six-dimensional space of rigid dimer geometries. The procedure is illustrated on results for the six best geometries for dimers of ethylene and of an indigoid heterocycle with 24 carbon, nitrogen, and oxygen atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Redox Behavior of 2,3-Diamino-1,4-naphthoquinone and its N-Alkylated Derivatives

Electrochemical reduction and oxidation potentials and standard heterogeneous electron transfer rate constants are reported for 2,3-diamino-1,4-naphthoquinone and two of its N-alkylated derivatives in acetonitrile. For two of the compounds, spectroelectrochemistry was used to obtain the absorption spectra of the radical cation and the radical anion. The compounds can be viewed as captodative biradicaloids and as such are of interest for photophysical studies of singlet fission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran

Two isomers of both the lowest excited singlet (S1) and triplet (T1) states of the directly para, para'-connected covalent dimer of the singlet-fission chromophore 1,3-diphenylisobenzofuran have been observed. In one isomer, excitation is delocalized over both halves of the dimer, and in the other, it is localized on one or the other half. For a covalent dimer in solution, such 'excitation isomerism' is extremely rare. The vibrationally relaxed isomers do not interconvert, and their photophysical properties, including singlet fission, differ significantly.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF – 4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a

14 SOLAR ENERGY↗
DOE OSTI2016

Imaging of conformational changes

Control of intramolecular conformational change in a small number of molecules or even a single one by an application of an outside electric field defined by potentials on nearby metal or dielectric surfaces has potential applications in both 3-D and 2-D nanotechnology. Specifically, the synthesis, characterization, and understanding of designed solids with controlled built-in internal rotational motion of a dipole promises a new class of materials with intrinsic dielectric, ferroelectric, optical and optoelectronic properties not found in nature. Controlled rotational motion is of great interest due to its expected utility in phenomena as diverse as transport, current flow in molecular junctions, diffusion in microfluidic channels, and rotary motion in molecular machines. A direct time-resolved observation of the dynamics of motion on ps or ns time scale in a single molecule would be highly interesting but is also very difficult and has yet to be accomplished. Much can be learned from an easier but still challenging comparison of directly observed initial and final orientational states of a single molecule, which is the basis of this project. The project also impacts the understanding of surface-enhanced Raman spectroscopy (SERS) and single-molecule spectroscopic detection, as well as the synthesis of solid-state materials with tailored properties from designed precursors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Singlet fission: Towards efficient solar cells

Singlet fission (SF) offers an opportunity to improve solar cell efficiency, but its practical use is hindered by the limited number of known efficient materials, limited knowledge of SF mechanism, mainly the relation between the dimer structure and SF efficiency and diffusion of the triplet states allowing injection of electrons into the solar cell semiconductor band. Here we report on our attempt to design new classes of chromophores and to study the relation between the structure and SF efficiency.

14 SOLAR ENERGY↗
DOE OSTI2014

Covalent Dimers of 1,3-Diphenylisobenzofuran for Singlet Fission: Synthesis and Electrochemistry

The synthesis of covalent dimers in which two 1,3-diphenylisobenzofuran units are connected through one phenyl substituent on each is reported. In three of the dimers, the subunits are linked directly, and in three others, they are linked via an alkane chain. A seventh new compound in which two 1,3-diphenylisobenzofuran units share a phenyl substituent is also described. These materials are needed for investigations of the singlet fission process, which promises to increase the efficiency of solar cells. The electrochemical oxidation and reduction of the monomer, two previously known dimers, and the seven new compounds have been examined, and reversible redox potentials have been compared with results obtained from density functional theory. In conclusion, although the overall agreement is satisfactory, some discrepancies are noted and discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Weak localization with nonlinear bosonic matter waves

We investigate the coherent propagation of dilute atomic Bose-Einstein condensates through irregularly shaped billiard geometries that are attached to uniform incoming and outgoing waveguides. Using the mean-field description based on the nonlinear Gross-Pitaevskii equation, we develop a diagrammatic theory for the self-consistent stationary scattering state of the interacting condensate, which is combined with the semiclassical representation of the single-particle Green function in terms of chaotic classical trajectories within the billiard. This analytical approach predicts a universal dephasing of weak localization in the presence of a small interaction strength between the atoms, which is found to be in good agreement with the numerically computed reflection and transmission probabilities of the propagating condensate. The numerical simulation of this quasi-stationary scattering process indicates that this interaction-induced dephasing mechanism may give rise to a signature of weak antilocalization, which we attribute to the influence of non-universal short-path contributions. - Highlights: Black-Right-Pointing-Pointer Numerical simulation of scattering of Bose-Einstein condensate through billiards. Black-Right-Pointing-Pointer Novel analytical semiclassical theory for nonlinear coherent scattering. Black-Right-Pointing-Pointer Inversion of weak localization due to mean-field interaction within the condensate. Black-Right-Pointing-Pointer Relevance of non-universal short-path contributions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗