Shortcuts to adiabaticity in the double well

123 p.

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

We theoretically describe in this work the n-type semiconducting behavior of a set of bis(arylene-ethynylene)-s-tetrazines ((ArCC)2Tz), by comparing their electronic properties with those of their parent diaryl-s-tetrazines (Ar2Tz) after the introduction of ethynylene bridges. The significantly reduced internal reorganization energy for electron transfer is ascribed to an extended delocalization of the LUMO for (ArCC)2Tz as opposite to that for Ar2Tz, which was described mostly localized on the s-tetrazine ring. The largest electronic coupling and the corresponding electron transfer rates found for bis(phenyl-ethynylene)-s-tetrazine, as well as for some halogenated derivatives, are comparable to those reported for the best performing n-type organic semiconductor materials such as diimides and perylenes. The theoretical mobilities for the studied compounds turn out to be in the range 0.3–1.3 cm2 V–1 s–1, close to values experimentally determined for common n-type organic semiconductors used in real devices. In addition, ohmic contacts can be expected when these compounds are coupled to metallic cathodes such as Na, Ca, and Sm. For these reasons, the future application of semiconducting bis(phenyl-ethynylene)-s-tetrazine and its fluorinated and brominated derivatives in optoelectronic devices is envisioned.

Non-parametrized functionals with empirical dispersion corrections: A happy match?

The performances of two parametrized functionals (namely B3LYP and B2PYLP) have been compared with those of two non-parametrized functionals (PBE0 and PBE0-DH) on a relatively large benchmark set when three different types of dispersion corrections are applied [namely the D2, D3 and D3(BJ) models]. Globally, the MAD computed using non-parametrized functionals decreases when adding dispersion terms although the accuracy not necessarily increases with the complexity of the model of dispersion correction used. In particular, the D2 correction is found to improve the performances of both PBE0 and PBE0-DH, while no systematic improvement is observed going from D2 to D3 or D3(BJ) corrections. Indeed when including dispersion, the number of sets for which PBE0-DH is the best performing functional decreases at the benefit of B2PLYP. Overall, our results clearly show that inclusion of dispersion corrections is more beneficial to parametrized double-hybrid functionals than to non-parametrized ones. The same conclusions globally hold for the corresponding global hybrids, showing that the marriage between non-parametrized functionals and empirical corrections may be a difficult deal.

Unraveling the performance of dispersion-corrected functionals for the accurate description of weakly bound natural polyphenols

Long-range non-covalent interactions play a key role in the chemistry of natural polyphenols. We have previously proposed a description of supramolecular polyphenol complexes by the B3P86 density functional coupled with some corrections for dispersion. We couple here the B3P86 functional with the D3 correction for dispersion, assessing systematically the accuracy of the new B3P86-D3 model using for that the well-known S66, HB23, NCCE31, and S12L datasets for non-covalent interactions. Furthermore, the association energies of these complexes were carefully compared to those obtained by other dispersion-corrected functionals, such as B(3)LYP-D3, BP86-D3 or B3P86-NL. Finally, this set of models were also applied to a database composed of seven non-covalent polyphenol complexes of the most interest.

Double Hybrid Functionals and the Π-System Bond Length Alternation Challenge: Rivaling Accuracy of Post-HF Methods

Predicting accurate bond length alternations (BLAs) in long conjugated oligomers has been a significant challenge for electronic-structure methods for many decades, made particularly important by the close relationships between BLA and the rich optoelectronic properties of π-delocalized systems. Here, we test the accuracy of recently developed, and increasingly popular, double hybrid (DH) functionals, positioned at the top of Jacobs Ladder of DFT methods of increasing sophistication, computational cost, and accuracy, due to incorporation of MP2 correlation energy. Our test systems comprise oligomeric series of polyacetylene, polymethineimine, and polysilaacetylene up to six units long. MP2 calculations reveal a pronounced shift in BLAs between the 6-31G(d) basis set used in many studies of BLA to date and the larger cc-pVTZ basis set, but only modest shifts between cc-pVTZ and aug-cc-pVQZ results. We hence perform new reference CCSD(T)/cc-pVTZ calculations for all three series of oligomers against which we assess the performance of several families of DH functionals based on BLYP, PBE, and TPSS, along with lower-rung relatives including global- and range-separated hybrids. Our results show that DH functionals systematically improve the accuracy of BLAs relative to single hybrid functionals. xDH-PBE0 (N4 scaling using SOS-MP2) emerges as a DH functional rivaling the BLA accuracy of SCS-MP2 (N5 scaling), which was found to offer the best compromise between computational cost and accuracy the last time the BLA accuracy of DFT- and wave function-based methods was systematically investigated. Interestingly, xDH-PBE0 (XYG3), which differs to other DHs in that its MP2 term uses PBE0 (B3LYP) orbitals that are not self-consistent with the DH functional, is an outlier of trends of decreasing average BLA errors with increasing fractions of MP2 correlation and HF exchange.

Theoretical Rationalization of the Singlet–Triplet Gap in OLEDs Materials: Impact of Charge-Transfer Character

New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Accurate Treatment of Large Supramolecular Complexes by Double-Hybrid Density Functionals Coupled with Nonlocal van der Waals Corrections

In this work, we present a thorough assessment of the performance of some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL) as well as their parent hybrid and GGA counterparts, in combination with the most modern version of the nonlocal (NL) van der Waals correction to describe very large weakly interacting molecular systems dominated by noncovalent interactions. Prior to the assessment, an accurate and homogeneous set of reference interaction energies was computed for the supramolecular complexes constituting the L7 and S12L data sets by using the novel, precise, and efficient DLPNO-CCSD(T) method at the complete basis set limit (CBS). The correction of the basis set superposition error and the inclusion of the deformation energies (for the S12L set) have been crucial for obtaining precise DLPNO-CCSD(T)/CBS interaction energies. Among the density functionals evaluated, the double-hybrid revPBE0-DH-NL and B2PLYP-NL with the three-body dispersion correction provide remarkably accurate association energies very close to the chemical accuracy. Overall, the NL van der Waals approach combined with proper density functionals can be seen as an accurate and affordable computational tool for the modeling of large weakly bonded supramolecular systems.

Systematic Improvement of Density Functionals through Parameter-Free Hybridization Schemes

It is suggested here that the ultimate accuracy of DFT methods arises from the type of hybridization scheme followed. This idea can be cast into a mathematical formulation utilizing an integrand connecting the noninteracting and the interacting particle system. We consider two previously developed models for it, dubbed as HYB0 and QIDH, and assess a large number of exchange-correlation functionals against the AE6, G2/148, and S22 reference data sets. An interesting consequence of these hybridization schemes is that the error bars, including the standard deviation, are found to markedly decrease with respect to the density-based (nonhybrid) case. This improvement is substantially better than variations due to the underlying density functional used. We thus finally hypothesize about the universal character of the HYB0 and QIDH models.

Modeling and analysis of thermoelectric energy conversion efficiency in nanostructures.

116 p.

Los orbitales en la educación química: un análisis mediante su representación gráfica

La constitución atómica de la materia está en la base de la química. Saber cómo se unen y cómo se separan los átomos es tener la clave de las transformaciones de la materia, que son el objeto de esta ciencia. Tendemos a imaginarnos a los átomos como pequeñas partículas, como bolitas, pero desde los años 1930 sabemos que no se puede entender su comportamiento microscópico mediante la física clásica. La mejor teoría que tenemos para este dominio es la mecánica cuántica, pero en ella la descripción más fundamental y completa de los sistemas no es a través de las variables clásicas, propias de las partículas, como la posición y el momento, sino de la función de onda. La función de onda es un objeto matemático que contiene toda la información del sistema. Sin embargo, ni extraer esa información ni interpretarla es sencillo, lo que supone una serie de problemas. Por ejemplo, casi noventa años después de su nacimiento la teoría cuántica apenas está presente en la enseñanza secundaria. Y el problema no afecta sólo al ámbito educativo. Por ejemplo, la química había desarrollado desde mediados del siglo XIX la teoría estructural, de enorme poder explicativo, que los químicos siguen empleando hoy en día. Además, si la función de onda de una partícula es un objeto extraño, la de un sistema de varias, como una molécula es, además, difícil de tratar matemáticamente. Pero la química necesitaba acceder a la estructura microscópica y a la reactividad de las moléculas... Mucho antes de que el avance de la computación pusiera a disposición de los químicos herramientas para resolver por la fuerza sus problemas, ya habían desarrollado modelos para incorporar la mecánica cuántica de forma relativamente sencilla a su arsenal y en esos modelos los protagonistas eran un tipo especial de funciones de onda, los orbitales. Los orbitales son funciones de onda de una sola partícula y por tanto mucho más sencillas de calcular e interpretar que las de los sistemas complejos. A cambio, no dan cuenta de todas las complejidades de una molécula, por ejemplo de las interacciones entre sus electrones. La química es una ciencia capaz de utilizar simultáneamente varios modelos diferentes e incluso contradictorios para cubrir su territorio y eso es lo que hizo, de más de una manera, con los orbitales, de origen cuántico, la teoría estructural clásica y los modelos semiclásicos del enlace a través de pares de electrones localizados. El resultado es un modelo híbrido y difícil de definir, pero eficaz, versátil, intuitivo, visualizable... y limitado, que se puede introducir incluso en niveles preuniversitarios. A pesar de eso, la enseñanza de los modelos cuánticos sigue siendo problemática. A los alumnos les resultan complicados y muchos expertos creen además que los confunden y mezclan con los clásicos. Se trata, pues de un problema abierto. Esta tesis tiene el propósito de dilucidar el papel de los orbitales en la educación química analizando casos de uso de sus representaciones gráficas, que son muy importantes en toda la química y aún más en estos modelos, que tienen un fuerte componente visual, analógico y metafórico. Los resultados de los análisis muestran una notable coherencia de uso de las imágenes de orbitales en enseñanza e investigación: En química los orbitales no son únicamente funciones matemáticas que se extienden por toda la molécula, sino también contenedores de electrones localizados que interaccionan por proximidad con transferencia de electrones Muchas veces estos modelos intuitivos se utilizan después de los cálculos cuánticos para interpretar los resultados en términos próximos a la química estructural. Aquí está la principal diferencia con los usos educativos: en la enseñanza, especialmente la introductoria, el modelo intuitivo tiende a ser el único que se usa.

SAFARI optical system architecture and design concept

SpicA FAR infrared Instrument, SAFARI, is one of the instruments planned for the SPICA mission. The SPICA mission is the next great leap forward in space-based far-infrared astronomy and will study the evolution of galaxies, stars and planetary systems. SPICA will utilize a deeply cooled 2.5m-class telescope, provided by European industry, to realize zodiacal background limited performance, and high spatial resolution. The instrument SAFARI is a cryogenic grating-based point source spectrometer working in the wavelength domain 34 to 230 μm, providing spectral resolving power from 300 to at least 2000. The instrument shall provide low and high resolution spectroscopy in four spectral bands. Low Resolution mode is the native instrument mode, while the high Resolution mode is achieved by means of a Martin-Pupplet interferometer. The optical system is all-reflective and consists of three main modules; an input optics module, followed by the Band and Mode Distributing Optics and the grating Modules. The instrument utilizes Nyquist sampled filled linear arrays of very sensitive TES detectors. The work presented in this paper describes the optical design architecture and design concept compatible with the current instrument performance and volume design drivers.