: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Broadening the optical absorption of organic photovoltaic (OPV) materials by enhancing the intramolecular push-pull effect is a general and effective method to improve the power conversion efficiencies of OPV cells. However, in terms of the electron acceptors, the most common molecular design strategy of halogenation usually results in down-shifted molecular energy levels, thereby leading to decreased open-circuit voltages in the devices. Herein, we report a chlorinated non-fullerene acceptor, which exhibits an extended optical absorption and meanwhile displays a higher voltage than its fluorinated counterpart in the devices. This unexpected phenomenon can be ascribed to the reduced non-radiative energy loss (0.206 eV). Due to the simultaneously improved short-circuit current density and open-circuit voltage, a high efficiency of 16.5% is achieved. This study demonstrates that finely tuning the OPV materials to reduce the bandgap-voltage offset has great potential for boosting the efficiency. Halogenation has proved an effective strategy to improve the power conversion efficiencies of organic solar cells but it usually leads to lower open-circuit voltages. Here, Cui et al. unexpectedly obtain higher open-circuit voltages and achieve a record high PCE of 16.5% by chlorination.

/pdf/over-16-efficiency-organic-photovoltaic-cells-enabled-by-a-4wvvibt9tt.pdf

Over 16% efficiency organic photovoltaic cells enabled by a chlorinated acceptor with increased open-circuit voltages

Quantitative analysis of molecular surface is a valuable technique for analyzing non-covalent interaction, studying molecular recognition mode, predicting reactive site and reactivity. An efficient way to realize the analysis was first proposed by Bulat et al. (J. Mol. Model., 16, 1679), in which Marching Tetrahedra (MT) approach commonly used in computer graphics is employed to generate vertices on molecular surface. However, it has been found that the computations of the electrostatic potential in the MT vertices are very expensive and some artificial surface extremes will be presented due to the uneven distribution of MT vertices. In this article, we propose a simple and reliable method to eliminate these unreasonably distributed surface vertices generated in the original MT. This treatment can save more than 60% of total analysis time of electrostatic potential, yet the loss in accuracy is almost negligible. The artificial surface extremes are also largely avoided as a byproduct of this algorithm. In addition, the bisection iteration procedure has been exploited to improve accuracy of linear interpolation in MT. The most appropriate grid spacing for surface analysis has also been investigated. 0.25 and 0.20 bohr are recommended to be used for surface analysis of electrostatic potential and average local ionization energy, respectively.

Quantitative analysis of molecular surface based on improved Marching Tetrahedra algorithm.

Red fluorescent molecules suffer from large, non-radiative internal conversion rates (kIC) governed by the energy gap law. To design efficient red thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs), a large fluorescence rate (kF) as well as a small energy difference between the lowest singlet and triplet excited states (ΔEST) is necessary. Herein, we demonstrated that increasing the distance between donor (D) and acceptor (A) in intramolecular-charge-transfer molecules is a promising strategy for simultaneously achieving small ΔEST and large kF. Four D-Ph-A-Ph-D-type molecules with an anthraquinone acceptor, phenyl (Ph) bridge, and various donors were designed, synthesized, and compared with corresponding D-A-D-type molecules. Yellow to red TADF was observed from all of them. The kF and ΔEST values determined from the measurements of quantum yield and lifetime of the fluorescence and TADF components are in good agreement with those predicted by corrected tim...

Anthraquinone-Based Intramolecular Charge-Transfer Compounds: Computational Molecular Design, Thermally Activated Delayed Fluorescence, and Highly Efficient Red Electroluminescence

The theorems at the core of density functional theory (DFT) state that the energy of a many-electron system in its ground state is fully defined by its electron density distribution. This connection is made via the exact functional for the energy, which minimizes at the exact density. For years, DFT development focused on energies, implicitly assuming that functionals producing better energies become better approximations of the exact functional. We examined the other side of the coin: the energy-minimizing electron densities for atomic species, as produced by 128 historical and modern DFT functionals. We found that these densities became closer to the exact ones, reflecting theoretical advances, until the early 2000s, when this trend was reversed by unconstrained functionals sacrificing physical rigor for the flexibility of empirical fitting.

https://science.sciencemag.org/content/sci/355/6320/49.full.pdf

Density functional theory is straying from the path toward the exact functional.

Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5) Plot density-of-states and spectrum. (6) Topology analysis for electron density. Some other useful utilities involved in quantum chemistry studies are also provided. The built-in graph module enables the results of wavefunction analysis to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com.

Multiwfn: a multifunctional wavefunction analyzer.

Multiwfn: a multifunctional wavefunction analyzer

An sp-hybridized all-carboatomic ring, cyclo[18]carbon: Electronic structure, electronic spectrum, and optical nonlinearity

Charge preservation is a necessary condition in population analysis. However, one such constraint is not enough to solve the arbitrariness involved in the population analysis such as Hirshfeld population. This arbitrariness results in too small Hirshfeld charges and poor reproducibility of molecular dipolar moments. In this article, the preservation of the molecular dipole moment is imposed upon the Hirshfeld population analysis as another constraint to improve the original Hirshfeld charges. In the scheme each atomic dipolar moment defined by the deformation density is expanded as contributions from all atoms in the molecule. The corresponding correction charges are then accumulated for each atom together with the original Hirshfeld charge as the predicted charge. All computed charges are generally larger than Hirshfeld charges, independent of basis set, and have very good electrostatic potential reproducibility and high correlation with the charges derived from the electrostatic potential fitting.

Tian Lu

Papers

Multiwfn: a multifunctional wavefunction analyzer.

Multiwfn: a multifunctional wavefunction analyzer

Quantitative analysis of molecular surface based on improved Marching Tetrahedra algorithm.

An sp-hybridized all-carboatomic ring, cyclo[18]carbon: Electronic structure, electronic spectrum, and optical nonlinearity

Atomic dipole moment corrected hirshfeld population method