Probing the wave function and dynamics of the quintet multiexciton state with coherent control in a singlet fission material

High-spin states play a key role in chemical reactions found in nature. In artificial molecular systems, singlet fission produces a correlated triplet-pair state, a spin-bearing excited state that can be harnessed for more efficient solar-energy conversion and photocatalysis. In particular, triplet-pair states with overall quintet character (total spin S=2) have been discovered, but many of the fundamental properties of these biexciton states remain unexplored. The net spin of these pair states makes spin-sensitive probes attractive for their characterization. Combined with their surprisingly long spin coherence (of order microseconds), this opens up techniques relying on coherent spin control. Here we apply coherent manipulation of triplet-pair states to (i) isolate their spectral signatures from coexisting free triplets and (ii) selectively couple quintet and triplet states to specific nuclear spins. Using this approach, we separate quintet and triplet transitions and extract the relaxation dynamics and hyperfine couplings of the fission-borne spin states. Our results highlight the distinct properties of correlated and free triplet excitons and demonstrate optically induced nuclear spin polarization by singlet fission

Photogeneration of Spin Quintet Triplet–Triplet Excitations in DNA-Assembled Pentacene Stacks

Singlet fission (SF), an exciton-doubling process observed in certain molecular semiconductors where two triplet excitons are generated from one singlet exciton, requires correctly tuned intermolecular coupling to allow separation of the two triplets to different molecular units. We explore this using DNA-encoded assembly of SF-capable pentacenes into discrete π-stacked constructs of defined size and geometry. Precise structural control is achieved via a combination of the DNA duplex formation between complementary single-stranded DNA and the local molecular geometry that directs the SF chromophores into a stable and predictable slip-stacked configuration, as confirmed by molecular dynamics (MD) modeling. Transient electron spin resonance spectroscopy revealed that within these DNA-assembled pentacene stacks, SF evolves via a bound triplet pair quintet state, which subsequently converts into free triplets. SF evolution via a long-lived quintet state sets specific requirements on intermolecular coupling, rendering the quintet spectrum and its zero-field-splitting parameters highly sensitive to intermolecular geometry. We have found that the experimental spectra and zero-field-splitting parameters are consistent with a slight systematic strain relative to the MD-optimized geometry. Thus, the transient electron spin resonance analysis is a powerful tool to test and refine the MD-derived structure models. DNA-encoded assembly of coupled semiconductor molecules allows controlled construction of electronically functional structures, but brings with it significant dynamic and polar disorders. Our findings here of efficient SF through quintet states demonstrate that these conditions still allow efficient and controlled semiconductor operation and point toward future opportunities for constructing functional optoelectronic systems

Deoxyribonucleic Acid Encoded and Size-Defined π-Stacking of Perylene Diimides

Natural photosystems use protein scaffolds to control intermolecular interactions that enable exciton flow, charge generation, and long-range charge separation. In contrast, there is limited structural control in current organic electronic devices such as OLEDs and solar cells. We report here the DNA-encoded assembly of π-conjugated perylene diimides (PDIs) with deterministic control over the number of electronically coupled molecules. The PDIs are integrated within DNA chains using phosphoramidite coupling chemistry, allowing selection of the DNA sequence to either side, and specification of intermolecular DNA hybridization. In this way, we have developed a “toolbox” for construction of any stacking sequence of these semiconducting molecules. We have discovered that we need to use a full hierarchy of interactions: DNA guides the semiconductors into specified close proximity, hydrophobic–hydrophilic differentiation drives aggregation of the semiconductor moieties, and local geometry and electrostatic interactions define intermolecular positioning. As a result, the PDIs pack to give substantial intermolecular π wave function overlap, leading to an evolution of singlet excited states from localized excitons in the PDI monomer to excimers with wave functions delocalized over all five PDIs in the pentamer. This is accompanied by a change in the dominant triplet forming mechanism from localized spin–orbit charge transfer mediated intersystem crossing for the monomer toward a delocalized excimer process for the pentamer. Our modular DNA-based assembly reveals real opportunities for the rapid development of bespoke semiconductor architectures with molecule-by-molecule precision

Two-point function of strangeness-carrying vector-currents in two-loop Chiral Perturbation Theory

We calculate the correlator between two external vector-currents having the quantum-numbers of a charged kaon. We give the renormalized expression to two loops in standard chiral perturbation theory in the isospin limit, which, as a physical result, is finite and scale-independent. Applications include a low energy theorem, valid at two loop order, of a flavor breaking combination of vector current correlators as well as a determination of the phenomenologically relevant finite $O(p^6)$-counterterm combination $Q_V$ by means of inverse moment finite energy sum rules. This determination is less sensitive to isospin-breaking effects than previous attempts.Comment: 24 pages, revtex, 4 figures, 2 tables, revised version, one ref. adde

QED Corrections to Neutrino Electron Scattering

We evaluate the O(alpha) QED corrections to the recoil electron energy spectrum in the process nu_l + e --> nu_l + e (+gamma), where (+gamma) indicates the possible emission of a photon and l=e, mu or tau. The soft and hard bremsstrahlung differential cross sections are computed for an arbitrary value of the photon energy threshold. We also study the O(alpha) QED corrections to the differential cross section with respect to the total combined energy of the recoil electron and a possible accompanying photon. Their difference from the corrections to the electron spectrum is investigated. We discuss the relevance and applicability of both radiative corrections, emphasizing their role in the analysis of precise solar neutrino electron scattering experiments.Comment: 14 pages + 10 figures. Minimal changes, published versio

Isospin Breaking in Neutron β\beta-decay and SU(3) Violation in Semi-leptonic Hyperon Decays

Present precision measurements of the neutron life time lead to a CKM matrix element $|V_{ud}|$ which is three standard deviations off the value inferred from heavy quark decays etc. We investigate the possibility whether isospin-breaking effects in the neutron-to-proton vector current transition matrix element $=1+\delta g_V$ could eventually close this gap. For that we calculate in chiral perturbation theory the effect of pion and kaon loops on the matrix element $$ taking into account the mass differences of the charged and neutral mesons. We find a negligibly small isospin-breaking effect of $\delta g_V \simeq -4 \cdot 10^{-5}$. The crucial quantity in the analysis of neutron beta-decay precision measurements is thus the radiative correction term $\Delta_R$. Furthermore, we calculate in heavy baryon chiral perturbation theory the SU(3) breaking effects on the vector transition charges of weak semi-leptonic hyperon decays. We find for these quantities channel-dependent relative deviations from the SU(3) limit which range from -10% to $+1$.Comment: 6 pages, 1 figure, to be published in Physical Review C (brief report

Probing the wave function and dynamics of the quintet multiexciton state with coherent control in a singlet fission material

High-spin states play a key role in chemical reactions found in nature. In artificial molecular systems, singlet fission produces a correlated triplet-pair state, a spin-bearing excited state that can be harnessed for more efficient solar-energy conversion and photocatalysis. In particular, triplet-pair states with overall quintet character (total spin S = 2 ) have been discovered, but many of the fundamental properties of these biexciton states remain unexplored. The net spin of these pair states makes spin-sensitive probes attractive for their characterization. Combined with their surprisingly long spin coherence (of order microseconds), this opens up techniques relying on coherent spin control. Here we apply coherent manipulation of triplet-pair states to (i) isolate their spectral signatures from coexisting free triplets and (ii) selectively couple quintet and triplet states to specific nuclear spins. Using this approach, we separate quintet and triplet transitions and extract the relaxation dynamics and hyperfine couplings of the fission-borne spin states. Our results highlight the distinct properties of correlated and free triplet excitons and demonstrate optically induced nuclear spin polarization by singlet fission

Orbit structure and (reversing) symmetries of toral endomorphisms on rational lattices

We study various aspects of the dynamics induced by integer matrices on the invariant rational lattices of the torus in dimension 2 and greater. Firstly, we investigate the orbit structure when the toral endomorphism is not invertible on the lattice, characterising the pretails of eventually periodic orbits. Next we study the nature of the symmetries and reversing symmetries of toral automorphisms on a given lattice, which has particular relevance to (quantum) cat maps.Comment: 29 pages, 3 figure

Skyrmion Quantization and the Decay of the Delta

We present the complete solution to the so-called ``Yukawa problem'' of the Skyrme model. This refers to the perceived difficulty of reproducing---purely from soliton physics---the usual pseudovector pion-nucleon coupling, echoed by pion coupling to the higher spin/isospin baryons $(I=J=3/2 , 5/2 , \cdots , N_c/2 )$ in a manner fixed by large-$N_c$ group theory. The solution involves surprisingly elegant interplay between the classical and quantum properties of a new configuration, the ``new improved skyrmion''. This is the near-hedgehog obtained by minimizing the usual skyrmion mass functional augmented by an all-important isorotational kinetic term. The numerics are pleasing: a $\Delta$ decay width within a few MeV of its measured value, and furthermore, the higher-spin baryons $(I=J \ge 5/2 )$ with widths so large ($\Gamma > 800 MeV$) that these undesirable large-$N_c$ artifacts effectively drop out of the spectrum, and pose no phenomenological problem. Beyond these specific results, we ground the Skyrme model in the Feynman Path Integral, and set up a transparent collective coordinate formalism that makes maximal use of the $1/N_c$ expansion. This approach elucidates the connection between skyrmions on the one hand, and Feynman diagrams in an effective field theory on the other.Comment: This TeX file inputs the macropackage harvmac.tex . Choose the ``b'' (big) option or equations will overrun