Molecules with enhanced electronic polarizabilities based on defect-like states in conjugated polymers

Highly conjugated organic polymers typically have large non-resonant electronic susceptibilities, which give the molecules unusual optical properties. To enhance these properties, defects are introduced into the polymer chain. Examples include light doping of the conjugated polymer and synthesis, conjugated polymers which incorporate either electron donating or accepting groups, and conjugated polymers which contain a photoexcitable species capable of reversibly transferring its electron to an acceptor. Such defects in the chain permit enhancement of the second hyperpolarizability by at least an order of magnitude

All-optical photochromic spatial light modulators based on photoinduced electron transfer in rigid matrices

A single material (not a multi-element structure) spatial light modulator may be written to, as well as read out from, using light. The device has tailorable rise and hold times dependent on the composition and concentration of the molecular species used as the active components. The spatial resolution of this device is limited only by light diffraction as in volume holograms. The device may function as a two-dimensional mask (transmission or reflection) or as a three-dimensional volume holographic medium. This device, based on optically-induced electron transfer, is able to perform incoherent to coherent image conversion or wavelength conversion over a wide spectral range (ultraviolet, visible, or near-infrared regions)

Molecular implementation of molecular shift register memories

An electronic shift register memory (20) at the molecular level is described. The memory elements are based on a chain of electron transfer molecules (22) and the information is shifted by photoinduced (26) electron transfer reactions. Thus, multi-step sequences of charge transfer reactions are used to move charge with high efficiency down a molecular chain. The device integrates compositions of the invention onto a VLSI substrate (36), providing an example of a molecular electronic device which may be fabricated. Three energy level schemes, molecular implementation of these schemes, optical excitation strategies, charge amplification strategies, and error correction strategies are described

Improved Efficiency of Open Quantum System Simulations Using Matrix Products States in the Interaction Picture

Modeling open quantum systems -- quantum systems coupled to a bath -- is of value in condensed matter theory, cavity quantum electrodynamics, nanosciences and biophysics. The real-time simulation of open quantum systems was advanced significantly by the recent development of chain mapping techniques and the use of matrix product states that exploit the intrinsic entanglement structure in open quantum systems. The computational cost of simulating open quantum systems, however, remains high when the bath is excited to high-lying quantum states. We develop an approach to reduce the computational costs in such cases. The interaction representation for the open quantum system is used to distribute excitations among the bath degrees of freedom so that the occupation of each bath oscillator is ensured to be low. The interaction picture also causes the matrix dimensions to be much smaller in a matrix product state of a chain-mapped open quantum system than in the Schr\"odinger picture. Using the interaction representation accelerates the calculations by 1-2 orders of magnitude over existing matrix-product-state method. In the regime of strong system-bath coupling and high temperatures, the speedup can be as large as 3 orders of magnitude. The approach developed here is especially promising to simulate the dynamics of open quantum systems in the high-temperature and strong-coupling regimes

A gradient-directed Monte Carlo approach to molecular design

The recently developed linear combination of atomic potentials (LCAP) approach [M.Wang et al., J. Am. Chem. Soc., 128, 3228 (2006)] allows continuous optimization in discrete chemical space and thus is quite useful in the design of molecules for targeted properties. To address further challenges arising from the rugged, continuous property surfaces in the LCAP approach, we develop a gradient-directed Monte Carlo (GDMC) strategy as an augmentation to the original LCAP optimization method. The GDMC method retains the power of exploring molecular space by utilizing local gradient information computed from the LCAP approach to jump between discrete molecular structures. It also allows random Monte Carlo moves to overcome barriers between local optima on property surfaces. The combined GDMC and LCAP approach is demonstrated here for optimizing nonlinear optical (NLO) properties in a class of donor-acceptor substituted benzene and porphyrin frameworks. Specifically, one molecule with four nitrogen atoms in the porphyrin ring was found to have a larger first hyperpolarizability than structures with the conventional porphyrin motif. 1Comment: 26 pages, 10 figure

Efficient simulation of open quantum systems coupled to a reservoir through multiple channels

The simulation of open quantum systems coupled to a reservoir through multiple channels remains a substantial challenge. This kind of open quantum system arises when considering the radiationless decay of excited states that are coupled to molecular vibrations, for example. We use the chain mapping strategy in the interaction picture to study systems linearly coupled to a harmonic bath through multiple interaction channels. In the interaction picture, the bare bath Hamiltonian is removed by a unitary transformation (the system-bath interactions remain), and a chain mapping transforms the bath modes to a new basis. The transformed Hamiltonian contains time-dependent local system-bath couplings. The open quantum system is coupled to a limited number of (transformed) bath modes in the new basis. As such, the entanglement generated by the system-bath interactions is local, making efficient dynamical simulations possible with matrix product states. We use this approach to simulate singlet fission, using a generalized spin-boson Hamiltonian. The electronic states are coupled to a vibrational bath both diagonally and off-diagonally. This approach generalizes the chain mapping scheme to the case of multi-channel system-bath couplings, enabling the efficient simulation of this class of open quantum systems using matrix product states.Comment: 6 pages, 4 figure

Documentos para a história de Portugal no século XX : a conjuntura do ano de 1946

Successfully predicting the frequency dispersion of electronic hyperpolarizabilities is an unresolved challenge in materials science and electronic structure theory. We show that the generalized Thomas−Kuhn sum rules, combined with linear absorption data and measured hyperpolarizability at one or two frequencies, may be used to predict the entire frequency-dependent electronic hyperpolarizability spectrum. This treatment includes two- and three-level contributions that arise from the lowest two or three excited electronic state manifolds, enabling us to describe the unusual observed frequency dispersion of the dynamic hyperpolarizability in high oscillator strength M-PZn chromophores, where (porphinato)zinc(II) (PZn) and metal(II)polypyridyl (M) units are connected via an ethyne unit that aligns the high oscillator strength transition dipoles of these components in a head-to-tail arrangement. We show that some of these structures can possess very similar linear absorption spectra yet manifest dramatically different frequency-dependent hyperpolarizabilities, because of three-level contributions that result from excited state-to-excited state transition dipoles among charge polarized states. Importantly, this approach provides a quantitative scheme to use linear optical absorption spectra and very limited individual hyperpolarizability measurements to predict the entire frequency-dependent nonlinear optical response

Quantum Simulation of Polarized Light-induced Electron Transfer with A Trapped-ion Qutrit System

Electron transfer within and between molecules is crucial in chemistry, biochemistry, and energy science. This study describes a quantum simulation method that explores the influence of light polarization on the electron transfer between two molecules. By implementing precise and coherent control among the quantum states of trapped atomic ions, we can induce quantum dynamics that mimic the electron transfer dynamics in molecules. We use $3$-level systems (qutrits), rather than traditional two-level systems (qubits) to enhance the simulation efficiency and realize high-fidelity simulations of electron transfer dynamics. We treat the quantum interference between the electron coupling pathways from a donor with two degenerate excited states to an acceptor and analyze the transfer efficiency. We also examine the potential error sources that enter the quantum simulations. The trapped ion systems have favorable scalings with system size compared to those of classical computers, promising access to electron-transfer simulations of increasing richness.Comment: 9 pages, 6 figure