Efficient quantum dynamics simulations of complex molecular systems: A unified treatment of dynamic and static disorder.

We present a unified and highly numerically efficient formalism for the simulation of quantum dynamics of complex molecular systems, which takes into account both temperature effects and static disorder. The methodology is based on the thermo-field dynamics formalism, and Gaussian static disorder is included into simulations via auxiliary bosonic operators. This approach, combined with the tensor-train/matrix-product state representation of the thermalized stochastic wave function, is applied to study the effect of dynamic and static disorders in charge-transfer processes in model organic semiconductor chains employing the Su-Schrieffer-Heeger (Holstein-Peierls) model Hamiltonian.

Transparent and Colorless Dye-Sensitized Solar Cells Exceeding 75% Average Visible Transmittance.

Most photovoltaic (PV) technologies are opaque to maximize visible light absorption. However, see-through solar cells open additional perspectives for PV integration. Looking beyond maximizing visible light harvesting, this work considers the human eye photopic response to optimize a selective near-infrared sensitizer based on a polymethine cyanine structure (VG20-C x ) to render dye-sensitized solar cells (DSSCs) fully transparent and colorless. This peculiarity was achieved by conferring to the dye the ability to strongly and sharply absorb beyond 800 nm (S0-S1 transition) while rejecting the upper S0-S n contributions far in the blue where the human retina is poorly sensitive. When associated with an aggregation-free anatase TiO2 photoanode, the selective NIR-DSSC can display 3.1% power conversion efficiency, up to 76% average visible transmittance (AVT), a value approaching the 78% AVT value of a standard double glazing window while reaching a color rendering index (CRI) of 92.1%. The ultrafast and fast charge transfer processes are herein discussed, clarifying the different relaxation channels from the dye monomer excited states and highlighting the limiting steps to provide future directions to enhance the performances of this nonintrusive NIR-DSSC technology.

Reliable Predictions of Benzophenone Singlet-Triplet Transition Rates: A Second-Order Cumulant Approach.

Fermi golden rule and second-order cumulant expansion of the time-dependent density matrix have been used to compute from first principles the rate of intersystem crossing in benzophenone, using minimum-energy geometries and normal modes of vibrations computed at the TDDFT/CAM-B3LYP level. Both approaches yield reliable values of the S1 decay rate, the latter being almost in quantitative agreement with the results of time-dependent spectroscopic measurements (0.154 ps-1 observed vs 0.25 ps-1 predicted). The Fermi golden rule slightly overestimates the decay rate of S1 state (kd = 0.45 ps-1) but provides better insights into the chemico-physical parameters, which govern the transition from a thermally equilibrated population of S1, showing that the indirect mechanism is much faster than the direct one because of the vanishingly small Franck-Condon weighted density of states at ΔE of transition.

Single-Stranded DNA Oligonucleotides Retain Rise Coordinates Characteristic of Double Helices.

The structures of single-stranded DNA oligonucleotides from dimeric to hexameric sequences have been thoroughly investigated. Computations performed at the density functional level of theory including dispersion forces and solvation show that single-stranded helices adopt conformations very close to crystallographic B-DNA, with rise coordinates amounting up to 3.3 Å. Previous results, suggesting that single strands should be shorter than double helices, largely originated from the incompleteness of the adopted basis set. Although sensible deviations with respect to standard B-DNA are predicted, computations indicate that sequences rich in stacked adenines are the most ordered ones, favoring the B-DNA pattern and inducing regular arrangements also on flanking nucleobases. Several structural properties of double helices rich in adenine are indeed already reflected by the corresponding single strands.

Hole Hopping Rates in Organic Semiconductors: A Second-Order Cumulant Approach.

Second-order cumulant expansion of the time dependent reduced density matrix has been employed to evaluate hole hopping rates in pentacene, tetracene, picene, and rubrene homodimers. The cumulant expansion is a full quantum mechanical approach, which enables the use of the whole set of nuclear coordinates in computations and the inclusion of both the effects of the equilibrium position displacements and of normal mode mixing upon hole transfer. The time dependent populations predicted by cumulant approach are in good agreement with those obtained by numerical solution of time dependent Schrödinger equation, even for ultrafast processes, where the Fermi Golden Rule fails.

Absorption Band Shapes of a Push-Pull Dye Approaching the Cyanine Limit: A Challenging Case for First Principle Calculations.

The absorption band shapes of a solvent tunable donor-acceptor dye have been theoretically investigated by using Kubo's generating function approach, with minimum energy geometries and normal coordinates computed at the DFT level of theory. The adopted computational procedure allows us to include in the computation of Franck-Condon factors the whole set of normal modes, without any limitation on excitation quanta, allowing for an almost quantitative reproduction of the absorption band shape when the equilibrium geometries of the ground and the excited states are well predicted by electronic computations. Noteworthy, the functionals that yield more accurate band shapes also provide good prediction of the moment variations upon excitation; because the latter quantities are rarely available, theoretical simulation of band shapes could be a powerful tool for choosing the most appropriate computational method for predictive purposes.