<i>Ab Initio</i> Calculation of the Ultraviolet–Visible (UV-vis) Absorption Spectrum, Electron-Loss Function, and Reflectivity of Solids

Ferrari, Anna Maria; Orlando, Roberto; Rérat, Michel

doi:10.1021/acs.jctc.5b00199

Cited by 55 publications

(57 citation statements)

References 53 publications

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“…1 limit of the static CPHF/KS calculations. In the present implementation, we take advantage of recent developments on the evaluation of "dynamic" dielectric properties of solids 31,43,44 to explicitly investigate the e↵ect of on computed piezo-optic constants.…”

Section: B the Automated Algorithmmentioning

confidence: 99%

Piezo-optic tensor of crystals from quantum-mechanical calculations

Erba

Ruggiero

Korter

et al. 2015

The Journal of Chemical Physics

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An automated computational strategy is devised for the ab initio determination of the full fourth-rank piezo-optic tensor of crystals belonging to any space group of symmetry. Elastic sti↵ness and compliance constants are obtained as numerical first derivatives of analytical energy gradients with respect to the strain and photo-elastic constants as numerical derivatives of analytical dielectric tensor components, which are in turn computed through a Coupled-Perturbed-Hartree-Fock/Kohn-Sham approach, with respect to the strain. Both point and translation symmetries are exploited at all steps of the calculation, within the framework of periodic boundary conditions. The scheme is applied to the determination of the full set of ten symmetry-independent piezo-optic constants of calcium tungstate CaWO 4 , which have recently been experimentally reconstructed. Present calculations unambiguously determine the absolute sign (positive) of the ⇡ 61 constant, confirm the reliability of 6 out of 10 experimentally determined constants and provide new, more accurate values for the remaining 4 constants. C 2015 AIP Publishing LLC. [http://dx

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Section: B the Automated Algorithmmentioning

confidence: 99%

Piezo-optic tensor of crystals from quantum-mechanical calculations

Erba

Ruggiero

Korter

et al. 2015

The Journal of Chemical Physics

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“…In the mentioned case the dependence of the emission features on the excitation wavelength was not explored, and the present study provides a complete characterization of the luminescence properties of [CuI( piperazine) 0.5 ] ∞ evidencing and discussing its dual behavior. In order to straighten out the fundamental physics underlying these phenomena, we have investigated the optical absorption properties of the crystalline [CuI( piperazine) 0.5 ] ∞ by means of theoretical calculations adopting a variant of a Time-Dependent Density Functional Theory (TD-DFT) method 30 recently implemented in the CRYSTAL quantum chemistry ab initio code (details in the ESI †). 31 In Fig.…”

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confidence: 99%

Dual luminescence in solid CuI(piperazine): hypothesis of an emissive 1-D delocalized excited state

Maini

Braga

Mazzeo³

et al. 2015

Dalton Trans.

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Solid [CuI( piperazine) 0.5 ] ∞ , characterized by a structure with an infinite double chain of CuI, presents an unexpected dual luminescence. The short copper-copper distances allow the existence of both cluster-centered and 1-D delocalized electronic transitions, as emerged from theoretical calculations. Beyond the more common cluster-centered emission a higher energy band, which differs in lifetime and in temperature dependence, is observed.One of the most prominent classes of luminescent coordination compounds is that of copper(I) halides, due to their promising features for application in the field of optoelectronics. [1][2][3][4][5] They are easily synthesized 6,7 and tunable in emission color, [8][9][10] with high emission quantum yields in the solid state. 7,10,11 Copper(I) halide compounds can be considered as a valid alternative to luminescent metal complexes of precious (i.e. Ir or Os) and rare earth metals, which are expensive and environmentally problematic. 12 The luminescence properties of the copper halide clusters arise from a remarkable variety of emissive states, which have been extensively investigated in the last 30 years and can be summarized as follows: (a) a low-energy emission, attributed to a triplet cluster-centered ( 3 CC) excited state, is observed in the case of metal center interactions [13][14][15][16][17][18][19] and is independent of the nature of the ligand engaged in the complex; (b) a highenergy emission, attributed to a triplet halide-to-ligand charge transfer ( 3 XLCT) excited state, may show up in the presence of unsaturated ligands with accessible π-orbitals. 20 Moreover, recent studies have shown that several copper compounds present a thermally activated delayed fluorescence (TADF): Cu(I) halide-bridged compounds with P^N ligands are characterized by (metal + halide)-to-ligand charge transfer ((M + X) LCT) excited states where the low singlet-triplet energy gap allows emission from both the singlet and the triplet excited states, depending on the temperature. [21][22][23] The structure of [CuI( piperazine) 0.5 ] ∞ 24 is characterized by a one-dimensional copper iodide polymeric structure. The infinite double chain of CuI is described as castellated, 25 as shown in Fig. 1a, and the tetrahedral coordination of the copper(I) ions is fulfilled by the bridging piperazine to construct a 3D network (Fig. 1b and c). The inorganic chain is generated by the sequence of an inversion center and 2-fold axis symmetry elements, thus two different copper distances are present (2.771(1) Å and 2.729(1) Å). Although the presence of infinite double chain motifs has been observed in 20 struc-

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“…The improvement of the accuracy of adiabatic timedependent density functional theory is an area of active research in condensed matter physics and physical chemistry [59,[82][83][84][85][86][87]; hence, we explored the application of Eq. (10) to time-dependent density functional theory (TDSX), and we show below that the SX functional can correctly reproduce not only ionization energies and fundamental gaps but also optical gaps.…”

Section: Resultsmentioning

confidence: 99%

Generalization of Dielectric-Dependent Hybrid Functionals to Finite Systems

et al. 2016

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The accurate prediction of electronic and optical properties of molecules and solids is a persistent challenge for methods based on density functional theory. We propose a generalization of dielectricdependent hybrid functionals to finite systems where the definition of the mixing fraction of exact and semilocal exchange is physically motivated, nonempirical, and system dependent. The proposed functional yields ionization potentials, and fundamental and optical gaps of many, diverse molecular systems in excellent agreement with experiments, including organic and inorganic molecules and semiconducting nanocrystals. We further demonstrate that this hybrid functional gives the correct alignment between energy levels of the exemplary TTF-TCNQ donor-acceptor system.

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Ab Initio Calculation of the Ultraviolet–Visible (UV-vis) Absorption Spectrum, Electron-Loss Function, and Reflectivity of Solids

Cited by 55 publications

References 53 publications

Piezo-optic tensor of crystals from quantum-mechanical calculations

Piezo-optic tensor of crystals from quantum-mechanical calculations

Dual luminescence in solid CuI(piperazine): hypothesis of an emissive 1-D delocalized excited state

Generalization of Dielectric-Dependent Hybrid Functionals to Finite Systems

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