Showing papers on "Excited state published in 2009"

The energy of charge-transfer states in electron donor-acceptor blends : insight into the energy losses in organic solar cells

Abstract: Here, a general experimental method to determine the energy ECT of intermolecular charge-transfer (CT) states in electron donor–acceptor (D–A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D–A blends to correct for a constant Coulombic term. It is shown that ECT correlates linearly with the open-circuit voltage (Voc) of photovoltaic devices in D–A blends via eVoc = ECT − 0.5 eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S1 with energy Eg) in the blend to the CT state (S1 → CT) occurs when Eg − ECT > 0.1 eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (ET) of D or A (CT → T1) can occur when ECT − ET > 0.1 eV. From these relations, it is concluded that in D–A blends optimized for photovoltaic action: i) the maximum attainable Voc is ultimately set by the optical band gap (eVoc = Eg − 0.6 eV) and ii) the singlet–triplet energy gap should be ΔEST < 0.2 eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area.

Observation of Rydberg blockade between two atoms

Abstract: When two single Rydberg atoms—those having electrons in highly excited states—interact, one can be used to control the quantum state of the other. Two independent experiments now demonstrate a ‘Rydberg blockade’, an effect that might make long-range quantum gates between neutral atoms possible. Blockade interactions whereby a single particle prevents the flow or excitation of other particles provide a mechanism for control of quantum states, including entanglement of two or more particles. Blockade has been observed for electrons1,2,3, photons4 and cold atoms5. Furthermore, dipolar interactions between highly excited atoms have been proposed as a mechanism for ‘Rydberg blockade’6,7, which might provide a novel approach to a number of quantum protocols8,9,10,11. Dipolar interactions between Rydberg atoms were observed several decades ago12 and have been studied recently in a many-body regime using cold atoms13,14,15,16,17,18. However, to harness Rydberg blockade for controlled quantum dynamics, it is necessary to achieve strong interactions between single pairs of atoms. Here, we demonstrate that a single Rydberg-excited rubidium atom blocks excitation of a second atom located more than 10 μm away. The observed probability of double excitation is less than 20%, consistent with a theoretical model of the Rydberg interaction augmented by Monte Carlo simulations that account for experimental imperfections.

DNA Excited-State Dynamics: From Single Bases to the Double Helix

Abstract: Ultraviolet light is strongly absorbed by DNA, producing excited electronic states that sometimes initiate damaging photochemical reactions. Fully mapping the reactive and nonreactive decay pathways available to excited electronic states in DNA is a decades-old quest. Progress toward this goal has accelerated rapidly in recent years, in large measure because of ultrafast laser experiments. Here we review recent discoveries and controversies concerning the nature and dynamics of excited states in DNA model systems in solution. Nonradiative decay by single, solvated nucleotides occurs primarily on the subpicosecond timescale. Surprisingly, excess electronic energy relaxes one or two orders of magnitude more slowly in DNA oligo- and polynucleotides. Highly efficient nonradiative decay pathways guarantee that most excited states do not lead to deleterious reactions but instead relax back to the electronic ground state. Understanding how the spatial organization of the bases controls the relaxation of excess electronic energy in the double helix and in alternative structures is currently one of the most exciting challenges in the field.

Unified treatment of quantum coherent and incoherent hopping dynamics in electronic energy transfer: reduced hierarchy equation approach.

Abstract: A new quantum dynamic equation for excitation energy transfer is developed which can describe quantum coherent wavelike motion and incoherent hopping in a unified manner. The developed equation reduces to the conventional Redfield theory and Forster theory in their respective limits of validity. In the regime of coherent wavelike motion, the equation predicts several times longer lifetime of electronic coherence between chromophores than does the conventional Redfield equation. Furthermore, we show quantum coherent motion can be observed even when reorganization energy is large in comparison to intersite electronic coupling (the Forster incoherent regime). In the region of small reorganization energy, slow fluctuation sustains longer-lived coherent oscillation, whereas the Markov approximation in the Redfield framework causes infinitely fast fluctuation and then collapses the quantum coherence. In the region of large reorganization energy, sluggish dissipation of reorganization energy increases the time electronic excitation stays above an energy barrier separating chromophores and thus prolongs delocalization over the chromophores.

A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states

Abstract: We introduce a hybrid density functional that asymptotically incorporates full Hartree-Fock exchange, based on the long-range-corrected exchange-hole model of Henderson et al. [J. Chem. Phys. 128, 194105 (2008)]. The performance of this functional, for ground-state properties and for vertical excitation energies within time-dependent density functional theory, is systematically evaluated, and optimal values are determined for the range-separation parameter, omega, and for the fraction of short-range Hartree-Fock exchange. We denote the new functional as LRC-omegaPBEh, since it reduces to the standard PBEh hybrid functional (also known as PBE0 or PBE1PBE) for a certain choice of its two parameters. Upon optimization of these parameters against a set of ground- and excited-state benchmarks, the LRC-omegaPBEh functional fulfills three important requirements: (i) It outperforms the PBEh hybrid functional for ground-state atomization energies and reaction barrier heights; (ii) it yields statistical errors comparable to PBEh for valence excitation energies in both small and medium-sized molecules; and (iii) its performance for charge-transfer excitations is comparable to its performance for valence excitations. LRC-omegaPBEh, with the parameters determined herein, is the first density functional that satisfies all three criteria. Notably, short-range Hartree-Fock exchange appears to be necessary in order to obtain accurate ground-state properties and vertical excitation energies using the same value of omega.

Observation of collective excitation of two individual atoms in the Rydberg blockade regime

Abstract: When two single Rydberg atoms—those with electrons in highly excited states—interact, one can be used to control the quantum state of the other. Two independent experiments demonstrate such ‘Rydberg blockade’, an effect that might make long-range quantum gates between neutral atoms possible.

Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex

Abstract: X-ray absorption spectroscopy is a powerful probe of molecular structure, but it has previously been too slow to track the earliest dynamics after photoexcitation. We investigated the ultrafast formation of the lowest quintet state of aqueous iron(II) tris(bipyridine) upon excitation of the singlet metal-to-ligand-charge-transfer ( 1 MLCT) state by femtosecond optical pump/x-ray probe techniques based on x-ray absorption near-edge structure (XANES). By recording the intensity of a characteristic XANES feature as a function of laser pump/x-ray probe time delay, we find that the quintet state is populated in about 150 femtoseconds. The quintet state is further evidenced by its full XANES spectrum recorded at a 300-femtosecond time delay. These results resolve a long-standing issue about the population mechanism of quintet states in iron(II)-based complexes, which we identify as a simple 1 MLCT→ 3 MLCT→ 5 T cascade from the initially excited state. The time scale of the 3 MLCT→ 5 T relaxation corresponds to the period of the iron-nitrogen stretch vibration.

Realization of an Excited, Strongly Correlated Quantum Gas Phase

Abstract: Ultracold atomic physics offers myriad possibilities to study strongly correlated many-body systems in lower dimensions. Typically, only ground-state phases are accessible. Using a tunable quantum gas of bosonic cesium atoms, we realized and controlled in one-dimensional geometry a highly excited quantum phase that is stabilized in the presence of attractive interactions by maintaining and strengthening quantum correlations across a confinement-induced resonance. We diagnosed the crossover from repulsive to attractive interactions in terms of the stiffness and energy of the system. Our results open up the experimental study of metastable, excited, many-body phases with strong correlations and their dynamical properties.

Dynamic Polarization of Single Nuclear Spins by Optical Pumping of Nitrogen-Vacancy Color Centers in Diamond at Room Temperature

Abstract: We report a versatile method to polarize single nuclear spins in diamond, based on optical pumping of a single nitrogen-vacancy (NV) defect and mediated by a level anticrossing in its excited state. A nuclear-spin polarization higher than 98% is achieved at room temperature for the 15N nuclear spin associated with the NV center, corresponding to microK effective nuclear-spin temperature. We then show simultaneous initialization of two nuclear spins in the vicinity of a NV defect. Such robust control of nuclear-spin states is a key ingredient for further scaling up of nuclear-spin based quantum registers in diamond.

Observation of ultralong-range Rydberg molecules

Abstract: In a Rydberg atom, at least one electron is excited into an orbital with a very high principal quantum number that extends the atom's electronic envelope far beyond the nucleus. Based on ideas introduced by Enrico Fermi in 1934, a recent piece of theoretical work predicted that the scattering of such an electron from a second atom in the ground-state could give rise to attractive interactions. This would yield giant molecules with internuclear separations reaching several thousand Bohr radii. The spectroscopic characterization of such ultra-long-range 'Rydberg molecules' is now reported. The molecules, ultracold rubidium dimers, have spectra in good agreement with model predictions. This achievement raises the exciting prospect of realizing other exotic molecular species such as the so-called trilobite molecules in the near future. A Rydberg atom has one electron excited into an orbital with a very high principal quantum number. The scattering of such an electron from a second atom in the ground state gives rise to long-range bonding, yielding giant molecules with internuclear separations reaching several thousand Bohr radii. Using s-state rubidium Rydberg atoms with quantum numbers between 34 and 40, Bendkowsky and colleagues have now spectroscopically characterized such 'Rydberg molecules', and measured their lifetimes and polarizabilities. Rydberg atoms have an electron in a state with a very high principal quantum number, and as a result can exhibit unusually long-range interactions. One example is the bonding of two such atoms by multipole forces to form Rydberg–Rydberg molecules with very large internuclear distances1,2,3. Notably, bonding interactions can also arise from the low-energy scattering of a Rydberg electron with negative scattering length from a ground-state atom4,5. In this case, the scattering-induced attractive interaction binds the ground-state atom to the Rydberg atom at a well-localized position within the Rydberg electron wavefunction and thereby yields giant molecules that can have internuclear separations of several thousand Bohr radii6,7,8. Here we report the spectroscopic characterization of such exotic molecular states formed by rubidium Rydberg atoms that are in the spherically symmetric s state and have principal quantum numbers, n, between 34 and 40. We find that the spectra of the vibrational ground state and of the first excited state of the Rydberg molecule, the rubidium dimer Rb(5s)–Rb(ns), agree well with simple model predictions. The data allow us to extract the s-wave scattering length for scattering between the Rydberg electron and the ground-state atom, Rb(5s), in the low-energy regime (kinetic energy, <100 meV), and to determine the lifetimes and the polarizabilities of the Rydberg molecules. Given our successful characterization of s-wave bound Rydberg states, we anticipate that p-wave bound states9, trimer states10 and bound states involving a Rydberg electron with large angular momentum—so-called trilobite molecules5—will also be realized and directly probed in the near future.

Charge-transfer excitons at organic semiconductor surfaces and interfaces.

Abstract: When a material of low dielectric constant is excited electronically from the absorption of a photon, the Coulomb attraction between the excited electron and the hole gives rise to an atomic H-like quasi-particle called an exciton. The bound electron-hole pair also forms across a material interface, such as the donor/acceptor interface in an organic heterojunction solar cell; the result is a charge-transfer (CT) exciton. On the basis of typical dielectric constants of organic semiconductors and the sizes of conjugated molecules, one can estimate that the binding energy of a CT exciton across a donor/acceptor interface is 1 order of magnitude greater than k(B)T at room temperature (k(B) is the Boltzmann constant and T is the temperature). How can the electron-hole pair escape this Coulomb trap in a successful photovoltaic device? To answer this question, we use a crystalline pentacene thin film as a model system and the ubiquitous image band on the surface as the electron acceptor. We observe, in time-resolved two-photon photoemission, a series of CT excitons with binding energies < or = 0.5 eV below the image band minimum. These CT excitons are essential solutions to the atomic H-like Schrodinger equation with cylindrical symmetry. They are characterized by principal and angular momentum quantum numbers. The binding energy of the lowest lying CT exciton with 1s character is more than 1 order of magnitude higher than k(B)T at room temperature. The CT(1s) exciton is essentially the so-called exciplex and has a very low probability of dissociation. We conclude that hot CT exciton states must be involved in charge separation in organic heterojunction solar cells because (1) in comparison to CT(1s), hot CT excitons are more weakly bound by the Coulomb potential and more easily dissociated, (2) density-of-states of these hot excitons increase with energy in the Coulomb potential, and (3) electronic coupling from a donor exciton to a hot CT exciton across the D/A interface can be higher than that to CT(1s) as expected from energy resonance arguments. We suggest a design principle in organic heterojunction solar cells: there must be strong electronic coupling between molecular excitons in the donor and hot CT excitons across the D/A interface.

Quasiclassical calculations of blackbody-radiation-induced depopulation rates and effective lifetimes of Rydberg nS , nP , and nD alkali-metal atoms with n≤80

Abstract: Rates of depopulation by blackbody radiation (BBR) and effective lifetimes of alkali-metal $nS$, $nP$, and $nD$ Rydberg states have been calculated in a wide range of principal quantum numbers $n\ensuremath{\le}80$ at the ambient temperatures of 77, 300, and 600 K. Quasiclassical formulas were used to calculate the radial matrix elements of the dipole transitions from Rydberg states. Good agreement of our numerical results with the available theoretical and experimental data has been found. We have also obtained simple analytical formulas for estimates of effective lifetimes and BBR-induced depopulation rates, which well agree with the numerical data.

On the generalized eigenvalue method for energies and matrix elements in lattice field theory

Abstract: We discuss the generalized eigenvalue problem for computing energies and matrix elements in lattice gauge theory, including effective theories such as HQET. It is analyzed how the extracted effective energies and matrix elements converge when the time separations are made large. This suggests a particularly efficient application of the method for which we can prove that corrections vanish asymptotically as exp(−(EN+1 − En) t). The gap EN+1 − En can be made large by increasing the number N of interpolating fields in the correlation matrix. We also show how excited state matrix elements can be extracted such that contaminations from all other states disappear exponentially in time. As a demonstration we present numerical results for the extraction of ground state and excited B-meson masses and decay constants in static approximation and to order 1/mb in HQET.

The formation of warm dense matter: experimental evidence for electronic bond hardening in gold

Abstract: Under strong optical excitation conditions, it is possible to create highly nonequilibrium states of matter. The nuclear response is determined by the rate of energy transfer from the excited electrons to the nuclei and the instantaneous effect of change in electron distribution on the interatomic potential energy landscape. We used femtosecond electron diffraction to follow the structural evolution of strongly excited gold under these transient electronic conditions. Generally, materials become softer with excitation. In contrast, the rate of disordering of the gold lattice is found to be retarded at excitation levels up to 2.85 megajoules per kilogram with respect to the degree of lattice heating, which is indicative of increased lattice stability at high effective electronic temperatures, a predicted effect that illustrates the strong correlation between electronic structure and lattice bonding.

Plasmonic Enhancement or Energy Transfer? On the Luminescence of Gold-, Silver-, and Lanthanide-Doped Silicate Glasses and Its Potential for Light-Emitting Devices

Abstract: With the technique of synchrotron X-ray activation, molecule-like, non-plasmonic gold and silver particles in soda-lime silicate glasses can be generated. The luminescence energy transfer between these species and Ianthanide(III) ions is studied. As a result, a significant lanthanide luminescence enhancement by a factor of up to 250 under non-resonant UV excitation is observed. The absence of a distinct gold and silver plasmon resonance absorption, respectively, the missing nanoparticle signals in previous SAXS and TEM experiments, the unaltered luminescence lifetime of the lanthanide ions compared to the non-enhanced case, and an excitation maximum at 300―350 nm (equivalent to the absorption range of small noble metal particles) indicate unambiguously that the observed enhancement is due to a classical energy transfer between small noble metal particles and lanthanide ions, and not to a plasmonic field enhancement effect. It is proposed that very small, molecule-like noble metal particles (such as dimers, trimers, and tetramers) first absorb the excitation light, undergo a singlet-triplet intersystem crossing, and finally transfer the energy to an excited multiplet state of adjacent lanthanide(III) ions. X-ray lithographic microstructuring and excitation with a commercial UV LED show the potential of the activated glass samples as bright light-emitting devices with tunable emission colors.

Excited state reactions in fluorescent proteins.

Abstract: The green fluorescent protein is a key technology in bioimaging. In this critical review, we consider how its various applications can be tailored from knowledge of the excited state chemistry. The photophysics of the basic chromophore in solution are described in detail, and the dominant radiationless decay mechanism is characterised. The quite different photophysics of wild type GFP are described next. The unique excited state proton transfer reaction observed can be used to model proton transfer processes in proteins. Examples where the proton transfer is blocked, or redirected to occur over a low short barrier H-bond are discussed. Finally the photophysics underlying the new generation of photochemically active fluorescent proteins are discussed (155 references).

Self-consistent-field calculations of core excited states.

Abstract: The accuracy of core excitation energies and core electron binding energies computed within a Delta self-consistent-field framework is assessed. The variational collapse of the core excited state is prevented by maintaining a singly occupied core orbital using an overlap criterion called the maximum overlap method. When applied to a wide range of small organic molecules, the resulting core excitation energies are not systematically underestimated as observed in time-dependent density functional theory and agree well with experiment. The accuracy of this approach for core excited states is illustrated by the calculation of the pre-edge features in x-ray absorption spectra of plastocyanin, which shows that accurate results can be achieved with Delta self-consistent-field calculations when used in conjunction with uncontracted basis functions.

Electronic acceleration of atomic motions and disordering in bismuth

Abstract: The development of X-ray and electron diffraction methods with ultrahigh time resolution has made it possible to map directly, at the atomic level, structural changes in solids induced by laser excitation. This has resulted in unprecedented insights into the lattice dynamics of solids undergoing phase transitions. In aluminium, for example, femtosecond optical excitation hardly affects the potential energy surface of the lattice; instead, melting of the material is governed by the transfer of thermal energy between the excited electrons and the initially cold lattice. In semiconductors, in contrast, exciting approximately 10 per cent of the valence electrons results in non-thermal lattice collapse owing to the antibonding character of the conduction band. These different material responses raise the intriguing question of how Peierls-distorted systems such as bismuth will respond to strong excitations. The evolution of the atomic configuration of bismuth upon excitation of its A(1g) lattice mode, which involves damped oscillations of atoms along the direction of the Peierls distortion of the crystal, has been probed, but the actual melting of the material has not yet been investigated. Here we present a femtosecond electron diffraction study of the structural changes in crystalline bismuth as it undergoes laser-induced melting. We find that the dynamics of the phase transition depend strongly on the excitation intensity, with melting occurring within 190 fs (that is, within half a period of the unperturbed A(1g) lattice mode) at the highest excitation. We attribute the surprising speed of the melting process to laser-induced changes in the potential energy surface of the lattice, which result in strong acceleration of the atoms along the longitudinal direction of the lattice and efficient coupling of this motion to an unstable transverse vibrational mode. That is, the atomic motions in crystalline bismuth can be electronically accelerated so that the solid-to-liquid phase transition occurs on a sub-vibrational timescale.

Excited-state spectroscopy of single NV defects in diamond using optically detected magnetic resonance

Abstract: Using pulsed optically detected magnetic resonance techniques, we directly probe electron-spin resonance transitions in the excited-state of single nitrogen-vacancy (NV) color centers in diamond. Unambiguous assignment of excited state fine structure is made, based on changes of NV defect photoluminescence lifetime. This study provides significant insight into the structure of the emitting 3 E excited state, which is invaluable for the development of diamond-based quantum information processing.

The Super of Superradiance

Abstract: In 1954, Robert Dicke introduced the concept of superradiance in describing the cooperative, spontaneous emission of photons from a collection of atoms. The concept of superradiance can be understood by picturing each atom as a tiny antenna emitting electromagnetic waves. Thermally excited atoms emit light randomly, and the emitted intensity is a function of the number of atoms, N . However, when the atomic “antennas” are coherently radiating in phase with each other, the net electromagnetic field is proportional to N , and therefore, the emitted intensity goes as N 2. As a result, the atoms radiate their energy N times faster than for incoherent emission. It is this anomalous radiance that Dicke dubbed “superradiance” ( 1 – 3 ).

Computation of accurate excitation energies for large organic molecules with double-hybrid density functionals

Abstract: Time-dependent double-hybrid density functional methods are evaluated for the calculation of vertical singlet–singlet valence excitation energies of a wide variety of organic molecules. Beside the already published TD-B2-PLYP method, an analogous approach based on the recently published ground state B2GP-PLYP functional is presented for the first time. Double-hybrid functionals contain a hybrid-GGA-like part for which a conventional TDDFT linear response treatment is carried out. The thus obtained excitation energies are afterwards corrected by adding a non-local correlation portion, which is based on an CIS(D) type excited state perturbative correction. Both, TD-B2-PLYP and TD-B2GP-PLYP, are first applied to the 142 vertical singlet excitation energies in a benchmark set by Schreiber et al., that contains small and medium sized organic molecules. In a second part, a new benchmark set composed of five large organic dyes is proposed. Accurate reference values are derived from experimental 0–0 excitation energies in solution. A back-correction scheme based on TDDFT computations is presented by which solvent, relaxation and vibrational effects are removed, yielding experimental vertical gas phase excitation energies with an estimated accuracy of about ±0.1 eV. The TD-B2-PLYP, TD-B2GP-PLYP and a variety of conventional TDDFT methods are then applied to this new benchmark set. The results for both considered test sets show that the new double-hybrid approaches yield the smallest mean absolute deviations of 0.22 eV for the first benchmark set and 0.19 eV (TD-B2-PLYP) and 0.16 eV (TD-B2GP-PLYP) for the new organic dye test set. Apart from a break-down of the perturbative correction for very high-lying transitions (larger than 8 eV), it is generally found that the double-hybrid functionals show high robustness and accuracy that cannot be obtained with conventional density functionals (e.g. B3-LYP).

Photodynamics in complex environments: ab initio multiple spawning quantum mechanical/molecular mechanical dynamics.

Abstract: Our picture of reactions on electronically excited states has evolved considerably in recent years, due to advances in our understanding of points of degeneracy between different electronic states, termed "conical intersections" (CIs). CIs serve as funnels for population transfer between different electronic states, and play a central role in ultrafast photochemistry. Because most practical photochemistry occurs in solution and protein environments, it is important to understand the role complex environments play in directing excited-state dynamics generally, as well as specific environmental effects on CI geometries and energies. In order to model such effects, we employ the full multiple spawning (FMS) method for multistate quantum dynamics, together with hybrid quantum mechanical/molecular mechanical (QM/MM) potential energy surfaces using both semiempirical and ab initio QM methods. In this article, we present an overview of these methods, and a comparison of the excited-state dynamics of several biological chromophores in solvent and protein environments. Aqueous solvation increases the rate of quenching to the ground state for both the photoactive yellow protein (PYP) and green fluorescent protein (GFP) chromophores, apparently by energetic stabilization of their respective CIs. In contrast, solvation in methanol retards the quenching process of the retinal protonated Schiff base (RPSB), the rhodopsin chromophore. Protein environments serve to direct the excited-state dynamics, leading to higher quantum yields and enhanced reaction selectivity.

Giant, level-dependent g factors in InSb nanowire quantum dots.

Abstract: We report on magnetotransport measurements on InSb nanowire quantum dots. The measurements show that the quantum levels of the InSb quantum dots have giant g factors, with absolute values up to approximately 70, the largest value ever reported for semiconductor quantum dots. We also observe that the values of these g factors are quantum level dependent and can differ strongly between different quantum levels. The presence of giant g factors indicates that considerable contributions from the orbital motion of electrons are preserved in the measured InSb nanowire quantum dots, while the level-to-level fluctuations arise from spin-orbit interaction. We have deduced a value of Delta(SO) = 280 mueV for the strength of spin-orbit interaction from an avoided level crossing between the ground state and first excited state of an InSb nanowire quantum dot with a fixed number of electrons.

Low temperature studies of the excited-state structure of negatively charged nitrogen-vacancy color centers in diamond.

Abstract: We report a study of the $^{3}E$ excited-state structure of single negatively charged nitrogen-vacancy (NV) defects in diamond, combining resonant excitation at cryogenic temperatures and optically detected magnetic resonance. A theoretical model is developed and shows excellent agreement with experimental observations. In addition, we show that the two orbital branches associated with the $^{3}E$ excited state are averaged when operating at room temperature. This study leads to an improved physical understanding of the NV defect electronic structure, which is invaluable for the development of diamond-based quantum information processing.

Enhancing the Quantum Properties of Manganese–Lanthanide Single‐Molecule Magnets: Observation of Quantum Tunneling Steps in the Hysteresis Loops of a {Mn12Gd} Cluster

Abstract: Single-molecule magnets (SMMs) are individual molecules that function as single-domain nanoscale magnetic particles. A SMM derives its properties from a combination of a high-spin ground state (S) and an easy axis type of magnetoanisotropy (negative zero-field splitting parameter,D), which results in a significant energy barrier to the reversal of the magnetization vector. Such species display both classical magnetization hysteresis, quantum tunneling of magnetization (QTM), and quantum phase interference. Thus, SMMs represent a molecular (“bottom-up”) route to nanoscale magnetism, with potential technological applications in information storage and spintronics at the molecular level, and use as quantum bits (qubits) in quantum computation by exploiting the QTM through the anisotropy barrier. The upper limit to the barrier (U) is given by S jD j or (S-1/4) jD j for integer and half-integer S, respectively. In practice, QTM through upper regions of the barrier makes the true or the effective barrier (Ueff) lower than that of U. Ideally, the QTM can be observed and studied in magnetization vs. DC (direct current) field hysteresis loops, appearing as distinct step-like features at periodic field values, at which levels on either side of the anisotropy barrier to relaxation are in resonance. The steps are thus field positions at which the magnetization relaxation rate increases owing to the onset of QTM. Such steps are a diagnostic signature of resonant QTM, and have been clearly seen only for a few classes of compounds, such as manganese, iron, and nickel SMMs. 7, 8] The most fruitful source of SMMs is the manganese carboxylate chemistry. The prototype was the [Mn12O12(O2CR)16(H2O)4] family, [2,4, 9] and a number of others have since been discovered; almost all have been transition metal clusters, and the vast majority of them have been manganese clusters containing at least some manganese(III) ions. As the search for new SMMs expanded, several groups explored mixed transition metal/lanthanide (Ln) compounds, and particularly Mn–Ln ones, as an attractive area; these efforts were greatly stimulated by the Cu2Tb2 SMM reported by Matsumoto and co-workers. The strategy is obviously to take advantage of the lanthanide ion s significant spin, and/or its large anisotropy, as reflected in a largeD value, to generate SMMs distinctly different from the homometallic ones. Indeed, there are now several Mn–Ln SMMs, including Mn11Ln4, [11] Mn11Gd2, [12] Mn5Ln4, [13a] and Mn6Dy6 [13b] . Many of them have exhibited magnetization hysteresis loops, but unfortunately none of them have displayed resolved QTM steps in these loops. Thus, the incorporation of lanthanide ions has led to a degradation of the quantum properties, as reflected in the QTM steps. The likeliest reason for the degradation of the quantum properties is the step broadening owing to the low-lying excited states resulting from very weak exchange interactions involving the 4f metal ion(s). Herein we report a new structural type in mixed Mn–Ln SMMs having a {Mn12Gd} 38+ core, in which clear QTM steps have been observed in the hysteresis loops of a mixed 3d–4f SMM for the first time. As a result, the D value of a 3d–4f SMM can be measured directly for the first time from the hysteresis data, that is, from magnetic field separation between the steps. The reaction of Mn(O2CPh)2, nBu4NMnO4, Gd(NO3)3, and PhCO2H in a 4:1:4:32 molar ratio in nitromethane produced a dark brown solution, which upon filtration and slow evaporation of the solvent resulted in crystals of [Mn12GdO9(O2CPh)18(O2CH)(NO3)(HO2CPh)] (1) in 40% yield. The structure of 1 consists of a {MnMn11} 35+ cluster with a central Gd ion (Figure 1). The {Mn12Gd} 38+ core is held together by seven m4-O 2 and two m3-O 2 ions. Peripheral ligation is provided by a m4-, three m3-, fourteen m-benzoate groups, a m3-formate group, a chelating NO3 on Mn12, and a terminal benzoic acid on Mn5. The formate probably comes from oxidation of nitromethane by the highly oxidizing MnO4 reagent. The metal oxidation states and the protonation levels of O ions were established by bond valence sum (BVS) calculations and the observation of manganese(III) Jahn–Teller (JT) elongation axes (Figure S1). All manganese atoms are six-coordinate, whereas the gadolinium [*] Dr. T. C. Stamatatos, Prof. Dr. G. Christou Department of Chemistry, University of Florida Gainesville, FL 32611-7200 (USA) Fax: (+1)352-392-8757 E-mail: christou@chem.ufl.edu

Near-Infrared-to-Blue Upconversion in Colloidal BaYF5:Tm3+, Yb3+ Nanocrystals

Abstract: Tetragonal barium yttrium fluoride (BaYF5) nanocrystals doped with 0.5 mol % Tm3+ and 15 mol % Yb3+ (BaYF5:Tm3+, Yb3+) were synthesized using the thermal decomposition method yielding rectangular-shaped nanocrystals (15 nm × 5 nm) that can (up)convert near-infrared light to higher energies such as blue, via a process known as upconversion. The upconversion spectrum of the BaYF5:Tm3+, Yb3+ nanocrystals, following excitation with 980 nm, revealed that the upconverted blue emission from the 1G4 → 3H6 transition was more intense than the infrared 3H4 → 3H6 emission at high excitation densities (90 W/cm2) contrary to what is normally observed for Tm3+/Yb3+ codoped nanomaterials. On the other hand, the infrared emission dominates at lower excitation densities (15 W/cm2) demonstrating a lack of excited Yb3+ ions to carry on the upconversion beyond the 3H4 excited state to the 1G4 excited state. A saturation of the upconversion process was observed in the power dependence studies at excitation densities above 57 ...

CdSe Quantum Dot Sensitized Solar Cells. Shuttling Electrons Through Stacked Carbon Nanocups

Abstract: The charge separation between excited CdSe semiconductor quantum dots and stacked-cup carbon nanotubes (SCCNTs) has been successfully tapped to generate photocurrent in a quantum dot sensitized solar cell (QDSC). By employing an electrophoretic deposition technique we have cast SCCNT−CdSe composite films on optically transparent electrodes (OTEs). The quenching of CdSe emission, as well as transient absorption measurements, confirms ultrafast electron transfer to SCCNTs. The rate constant for electron transfer increases from 9.51 × 109 s−1 to 7.04 × 1010 s−1 as we decrease the size of CdSe nanoparticles from 4.5 to 3 nm. The ability of SCCNTs to collect and transport electrons from excited CdSe has been established from photocurrent measurements. The morphological and excited state properties of SCCNT−CdSe composites demonstrate their usefulness in energy conversion devices.

Coherent coupling between surface plasmons and excitons in semiconductor nanocrystals

Abstract: We present an experimental demonstration of strong coupling between a surface plasmon propagating on a planar silver substrate, and the lowest excited state of CdSe nanocrystals. Variable-angle spectroscopic ellipsometry measurements demonstrated the formation of plasmon-exciton mixed states, characterized by a Rabi splitting of $\sim$ 82 meV at room temperature. Such a coherent interaction has the potential for the development of plasmonic non-linear devices, and furthermore, this system is akin to those studied in cavity quantum electrodynamics, thus offering the possibility to study the regime of strong light-matter coupling in semiconductor nanocrystals at easily accessible experimental conditions.

Explanation of photon correlations in the far-off-resonance optical emission from a quantum-dot-cavity system.

Abstract: In a coupled quantum-dot–nanocavity system, the photoluminescence from an off-resonance cavity mode exhibits strong quantum correlations with the quantum-dot transitions, even though its autocorrelation function is classical. Using new pump-power dependent photon-correlation measurements, we demonstrate that this seemingly contradictory observation that has so far defied an explanation stems from cascaded cavity photon emission in transitions between excited multiexciton states. The mesoscopic nature of quantum-dot confinement ensures the presence of a quasicontinuum of excitonic transitions, part of which overlaps with the cavity resonance.

Reconsideration of the excited-state double proton transfer (ESDPT) in 2-aminopyridine/acid systems: role of the intermolecular hydrogen bonding in excited states.

Abstract: In the present work, the excited-state double proton transfer (ESDPT) in 2-aminopyridine (2AP)/acid systems has been reconsidered using the combined experimental and theoretical methods. The steady-state absorption and fluorescence spectra of 2AP in different acids, such as formic acid, acetic acid, propionic acid, etc. have been measured. We demonstrated for the first time that the ESDPT reaction can take place between 2AP and all of these acids due to the formation of the intermolecular double hydrogen bonds. Furthermore, the vitally important role of the intermolecular double hydrogen bonds between 2AP and acids for ESDPT reaction has also been confirmed by the disappearance of ESDPT when we add the polar acetonitrile to the 2AP/acids systems. This may be due to that the respective polar solvation of 2AP and acids by the acetonitrile solvent disrupts the formation of intermolecular double hydrogen bonds between 2AP and acids. Moreover, the intermolecular double hydrogen bonds are demonstrated to be significantly strengthened in the electronic excited state of 2AP/acid systems using the time-dependent density functional theory (TDDFT) method. The ESDPT reaction is facilitated by the electronic excited-state hydrogen bond strengthening. In addition, potential energy curves of the electronic excited state along the proton transfer coordinate are also calculated by the TDDFT method. The stepwise mechanism of the ESDPT reaction in the 2AP/acid systems is theoretically reconfirmed, and the concerted mechanism is theoretically excluded. At the same time, the sequence of the double proton transfers is theoretically clarified for the first time using the potential energy curves calculated by TDDFT method.