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Nuclear spin-induced circular dichroism (NSCD) is a molecular effect of differential absorption of left- and right-circularly polarized light due to nuclear spins in the molecule. In this work, new tools for its calculation are presented. Specifically, analytic expressions for the computation of the K term of NSCD have been derived and implemented for the second-order coupled cluster singles and doubles (CC2) model. NSCD results obtained thereby for three derivatives of azobenzenes have been compared with results from time-dependent density functional theory (TD-DFT). The complementary information that could be obtained from NSCD measurements compared to NMR for these three species is discussed. [ABSTRACT FROM AUTHOR]

This work employs the correlated wavefunction-based methods ADC(2) and CC2 in combination with the implicit solvent model COSMO to calculate the UV/Vis absorption and fluorescence emission energies of particularly strong hydroxypyrene photoacids in acetone. According to the Förster cycle, the electronic transition energies are first used to compute , i.e., the pKa change upon excitation and then the excited-state pKa (labeled) with ground-state pKa values based on COSMO-RS as additional inputs. Furthermore, for the strongest photoacid of that class, namely tris(1,1,1,3,3,3-hexafluoropropan-2-yl)-8-hydroxypyrene-1,3,6-trisulfonate, the need to go beyond implicit solvation and to account for explicit solvent effects on the electronic transition energies and the resulting ΔpKa is investigated in the solvents acetone, dimethyl sulfoxide (DMSO), and water. For this, a hybrid implicit–explicit approach is followed by comparing micro-solvated structures that are generated based on Kamlet–Taft considerations. While implicit solvent effects are mostly sufficient for the aprotic solvent acetone, one explicit solvent molecule seems relevant for DMSO due to its stronger hydrogen-bond (HB) acceptance and hence larger interaction with the photoacid OH group as a HB donor. For the protic solvent water, the situation is more complicated, involving at least one water molecule at the OH group and up to three water molecules at the O− group of the corresponding base. Finally, these results are used to rationalize the experimentally observed spectral evolution of the photoacid absorption band in acetone–water solvent mixtures. [ABSTRACT FROM AUTHOR]

Iron and cobalt-based oxides crystallizing in the spinel structure are efficient and affordable catalysts for the oxidation of organics, yet, the detailed understanding of their surface structure and reactivity is limited. To fill this gap, we have investigated the (001) surfaces of cobalt ferrite, CoFe2O4, with the A- and B-layer terminations using density functional theory (DFT/PBE0) and an embedded cluster model. We have considered the five-fold coordinated Co2+/3+ (Oh), two-fold coordinated Fe2+ (Td), and an oxygen vacancy, as active sites for the adsorption of water and short-chain alcohols: methanol, ethanol, and 2-propanol, in the low coverage regime. The adsorbates dissociate upon adsorption on the Fe sites whereas the adsorption is mainly molecular on Co. At oxygen vacancies, the adsorbates always dissociate, fill the vacancy and form (partially) hydroxylated surfaces. The computed vibrational spectra for the most stable configurations are compared with results from diffuse reflectance infrared Fourier transform spectroscopy. [ABSTRACT FROM AUTHOR]

We investigate how the absorption and fluorescence of halogenated imidazolium compounds in acetonitrile solution is influenced by the presence of counterions and the ability to act as halogen-bond donors. Experimental measurements and quantum chemical calculations with correlated wavefunction methods are applied to study three monodentate halogen-bond complexes of iodo-imidazolium, iodo-benzimidazolium and bromo-benzimidazolium cations with triflate counterions, and a bidentate complex of bis(iodo-benzimidazolium) dications with chloride as counterion. The three monodentate complexes with triflate counterions relax after photoexcitation to minima on the S1 potential energy surface where the C–I bond and the I⋯O halogen bond are partially broken. For the bidentate complex with the smaller chloride counterion the halogen-bond interaction stays intact in the S1 minimum that is reached by relaxation from the Franck–Condon point. In a complementing experimental approach, stationary absorption and emission as well as transient fluorescence spectra are recorded for iodo- and bromo-benzimidazolium in acetonitrile. Variation of the counterion, substitution of the iodine by bromine, hydrogen, or methyl, and the comparison to theory allows the identification of spectroscopic signatures and photoinduced dynamics associated with ion-pairing. [ABSTRACT FROM AUTHOR]

Pd nanoparticles deposited on nitrogen-doped mesoporous carbon are promising catalysts for highly selective and effective catalytic hydrogenation reactions. To design and utilize these novel catalysts, it is essential to understand the effect of N doping on the metal–support interactions. A combined experimental (X-ray photoelectron spectroscopy) and computational (density functional theory) approach is used to identify preferential adsorption sites and to give detailed explanations of the corresponding metal–support interactions. Pyridinic N atoms turned out to be the preferential adsorption sites for Pd nanoparticles on nitrogen-doped mesoporous carbon, interacting through their lone pairs (LPs) with the Pd atoms via N-LP – Pd dσ and N-LP – Pd s and Pd dπ – π* charge transfer, which leads to a change in the Pd oxidation state. Our results evidence the existence of bifunctional palladium nanoparticles containing Pd0 and Pd2+ centers. [ABSTRACT FROM AUTHOR]

A key step for achieving better insight into catalytic hydrogenation reactions is to understand in detail the process of hydrogen adsorption on the catalyst. The present article focuses on hydrogen adsorption on carbon-supported palladium clusters, which are nowadays one of the most common catalysts in industrial applications. Density functional theory is applied to study Pd6 and Pd21 clusters to reveal the influence of the carbon support material on the properties of the catalyst as well as on the mechanisms and energetics of the hydrogen adsorption. In general, a stepwise hydrogen adsorption process is observed consisting of molecular adsorption followed by dissociative chemisorption. The carbon support material does not noticeably affect the reaction mechanisms, but has a large influence on energy barriers and preferential adsorption sites. Our comparison of Pd6 and Pd21 systems reveals that small clusters, such as Pd6, are able to model some but not all important properties of palladium nanoparticles and, therefore, it is essential to also study larger cluster sizes. [ABSTRACT FROM AUTHOR]

Analytic second nuclear derivatives for excited electronic state energies have been implemented for the resolution-of-the-identity accelerated CC2, CIS(D∞) and ADC(2) models. Our efficient implementation with 풪(풩2) memory demands enables the treatment of medium sized molecules with large basis sets and high numerical precision and thereby paves the way for semi-numerical evaluation of the higher-order derivatives required for anharmonic corrections to excited state vibrational frequencies. We compare CC2 harmonic and anharmonic excited state frequencies with experimental values for para-difluorobenzene, toluene and catechol. Basis set problems occur for out-of-plane bending vibrations due to intramolecular basis set superposition error. For non-planar molecules and in plane modes of planar molecules, the agreement between theory and experiment is better than 30 cm−1 on average and we reassign a number of experimental bands on the basis of the ab initio predictions. [ABSTRACT FROM AUTHOR]

Understanding deactivation mechanisms of functional groups is a key step to design novel photo-active devices and molecular imaging agents. Here, we elucidate the photochemistry of linear triazenes, an extended analogue of the photo-switchable azo group, exemplarily for the widely used DNA-minor-groove binder berenil. Combining ultrafast spectroscopy and ab initio calculations unveils that the E-azo,s-trans structure of berenil predominates in the gas phase and in aqueous solution, and ADC(2) intrinsic reaction coordinate calculations disclose that the excited-state relaxation to the S1 minima/conical intersections follows a two-step mechanism: N=N bond stretching followed by a bicycle-pedal rotation in the triazene bridge. Furthermore, studying the ground-state pathways shows that a fraction of the molecules relaxes back to the E-azo,s-trans isomer while the other part photoisomerizes to the Z-azo,s-trans via a hula-twist motion, as evidenced by experimental quantum yields of Φ≈ 0.5 found for berenil in water, ethylene glycol, or bound to β-trypsin. Moreover, our studies show that while the excited-state relaxation is insensitive to the environment, the ground-state dynamics depend on biomolecular binding partners. [ABSTRACT FROM AUTHOR]

We report the first calculations of rotational strengths for circularly polarised phosphorescence at the coupled cluster level. The rotational strengths for circular dichroism (CD), circularly polarised fluorescence (CPF) and circularly polarised phosphorescence (CPP) were calculated for β,γ-enones and ketones with conjugated double bonds using the CC2 model. To compute spin-forbidden CPP, spin–orbit coupling with perturbation theory is employed within a response theory framework (SOC-PT-CC2). For closed-shell molecules containing only light elements, a spin-free formalism is used to treat the singlet–triplet transitions. It is verified that the simplification obtained in the spin-free formulation from the Wigner–Eckart theorem for spin-forbidden oscillator strengths is also valid for the rotational strengths. Our implementation utilises the resolution of identity (RI) approximation for two-electron integrals which facilitates applications to larger molecules. In the current study, the rotational strength for spin-forbidden circularly-polarised phosphorescence was calculated for a chiral aromatic system, S-DMBDA, containing 44 atoms. [ABSTRACT FROM AUTHOR]

We present an implementation of analytic gradients for electronically excited states for the algebraic-diagrammatic construction through second order, ADC(2), in combination with the conductor-like screening model (COSMO) as an implicit solvent model. The implementation uses a post-SCF reaction field scheme for the coupling between the environment and the quantum system which retains the computational efficiency of the gas-phase RI-ADC(2) calculations. Applying this approach, we computed solvatochromic shifts for UV absorption and fluorescence transitions of 4-(N,N-dimethylamino)benzonitrile using equilibrium geometries for the ground and the first excited states optimized in the presence of acetonitrile as solvent. Furthermore, we investigated the excited state energies and geometries of the 2-iodobenzimidazolium·triflate ion pair in aqueous solution as an example where solvent effects have a large influence on the structure and the UV spectrum. [ABSTRACT FROM AUTHOR]

We present the first origin-independent approach for the treatment of two-photon circular dichroism (TPCD) using coupled cluster methods. The approach is assessed concerning its behavior on the choice of the basis set and different coupled cluster methods. We also provide a comparison of results from CC2 with those from density functional theory using the CAM-B3LYP functional. Concerning the basis set we note that in most cases an augmented triple zeta basis or a doubly augmented double zeta basis is needed for reasonably converged results. In the comparison of different coupled cluster methods results from CCSD, CC3 and CC2 have been found to be quite similar in most cases, while CCS results differ remarkably from the results at the higher levels. However, this proof-of-principle study also shows that further benchmarking of DFT and CC2 against accurate coupled cluster reference values (e.g. CCSD or CC3) is needed. [ABSTRACT FROM AUTHOR]

We present our current progress on the combination of explicit electron correlation with the pair natural orbital (PNO) representation. In particular we show cubic scaling PNO-MP2-F12, UGRAPHIC DISPLAY="INLINE" ID="UGT1" SRC="UGT1"/ and PNO-CCSD[F12] implementations. The PNOs are constructed using a hybrid scheme, where the PNOs are generated in a truncated doubles space, spanned by orbital specific virtuals obtained using an iterative eigenvector algorithm. We demonstrate the performance of our implementation through calculations on a series of glycine chains. The accuracy of the local approximations is assessed using the S66 benchmark set, and we report for the first time explicitly correlated CCSD results for the whole set and improved estimates for the CCSD/CBS limits. For several dimers the PNO-CCSD[F12] calculations are more accurate than the current reference values. Additionally, we present pilot applications of our PNO-CCSD[F12] code to host–guest interactions in a cluster model for zeolite H-ZSM-5 and in a calix[4]arene–water complex. [ABSTRACT FROM AUTHOR]

We investigate the performance of the approximate coupled cluster singles- and doubles model CC2 in the prediction of optical rotations of organic molecules. For this purpose we employ a combination of two test sets from the literature which include small and medium-sized rigid organic molecules and a series of helicenes. CC2 calculations on molecules as large as 11-helicene became possible through a recent implementation of frequency-dependent second-order properties for CC2 which makes use of the resolution-of-the-identity approximation for the electron repulsion integrals. The results are assessed with respect to the accuracy of the absolute values of the optical rotation and the prediction of the correct sign, which is crucial for the determination of absolute configurations. The performance of CC2 is compared with that of density functional theory at the B3LYP and CAM-B3LYP levels. Furthermore we investigated the influence of the molecular geometry and the one-electron basis set and tested to which extent spin-component scaling changes the results. [ABSTRACT FROM AUTHOR]