Search Results (7)

The mechanism features of colloidal quantum dots (QDs) passivation with thioglycolic acid molecules (TGA) for cases of different luminescent properties is considered using FTIR. This problem is considered based on FTIR spectra analysis for various ionic forms of TGA. Experimental TGA molecules FTIR spectra is interpreted, basing on the data on modeling of TGA vibrational modes, realized in the framework of density functional method (DFT /B3LYP/6-31+G(d)) taking into account the vibrations anharmonicity of every functional group. This approach provides a significant improvement in the agreement between the experimental and calculated data. FTIR spectra of Ag ${}_2$ S/TGA QDs with exciton and recombination luminescence are differ from each other and B “freeB” TGA molecules. The $\nu (S-H)$ TGA peak (2559 cm ${}^{-1}$ ) disappears in FTIR spectra of Ag ${}_2$ S/TGA QD samples. This fact indicates the interactions between TGA thiol group and dangling bonds of Ag ${}_2$ S nanocrystals. Ag ${}_2$ S QDs passivation with TGA molecules leads to emergence ${\nu }_{as}$ (COO ${}^{-}$ ) (1584 cm ${}^{-1}$ ) and ${\nu }_s$ (COO ${}^{-}$ ) (1387 cm ${}^{-1}$ ) peaks. It indicates TGA adsorption in ionic form. For Ag ${}_2$ S/TGA QDs with exciton luminescence we observed (a) significant low-frequency shift of ${\nu }_s$ (COO ${}^{-}$ ) peak from 1388 cm ${}^{-1}$ to 1359 cm ${}^{-1}$ and high-frequency shift of ${\nu }_{as}$ (COO ${}^{-}$ ) peak from 1567 cm ${}^{-1}$ to 1581 cm ${}^{-1}$ ; (b) change in the ratio of intensities of ${\nu }_{as}$ (COO ${}^{-}$ ) and ${\nu }_s$ (COO ${}^{-}$ ) vibrations. This feature is caused by the change in the symmetry of TGA molecules due to passivation of Ag ${}_2$ S quantum dots.For Ag ${}_2$ S/TGA QDs with recombination luminescence, the insignificant high-frequency shift of 7–10 cm ${}^{-1}$ for ${\nu }_{as}$ (COO ${}^{-}$ ) at 1567 cm ${}^{-1}$ and low-frequency shift of 3–5 cm ${}^{-1}$ for ${\nu }_s$ (COO ${}^{-}$ ) at 1388 cm ${}^{-1}$ , probably caused by the interaction of thiol with Ag ${}_2$ S surface is observed. Using FTIR spectra, it was found that IR luminescence photodegradation is also accompanied by changes in the thioglycolic acid molecules, which capped Ag ${}_2$ S QDs. In the case of Ag ${}_2$ S QDs with exciton luminescence, the degradation process is non-reversible. It is accompanied by TGA photodegradation with the formation of $\alpha$ -thiol-substituted acyl radical (S-CH ${}_2$ -CO ${}^{•}$ ) TGA. Full article

During the last decades, the Nonequilibrium Green’s function (NEGF) formalism has been proposed to develop nano-scaled device-simulation tools since it is especially convenient to deal with open device systems on a quantum-mechanical base and allows the treatment of inelastic scattering. In particular, it is able to account for inelastic effects on the electronic and thermal current, originating from the interactions of electron–phonon and phonon–phonon, respectively. However, the treatment of inelastic mechanisms within the NEGF framework usually relies on a numerically expensive scheme, implementing the self-consistent Born approximation (SCBA). In this article, we review an alternative approach, the so-called Lowest Order Approximation (LOA), which is realized by a rescaling technique and coupled with Padé approximants, to efficiently model inelastic scattering in nanostructures. Its main advantage is to provide a numerically efficient and physically meaningful quantum treatment of scattering processes. This approach is successfully applied to the three-dimensional (3D) atomistic quantum transport OMEN code to study the impact of electron–phonon and anharmonic phonon–phonon scattering in nanowire field-effect transistors. A reduction of the computational time by about ×6 for the electronic current and ×2 for the thermal current calculation is obtained. We also review the possibility to apply the first-order Richardson extrapolation to the Padé N/N − 1 sequence in order to accelerate the convergence of divergent LOA series. More in general, the reviewed approach shows the potentiality to significantly and systematically lighten the computational burden associated to the atomistic quantum simulations of dissipative transport in realistic 3D systems. Full article

The effect of isotopic substitution on near-infrared (NIR) spectra has not been studied in detail. With an exception of few major bands, it is difficult to follow the spectral changes due to complexity of NIR spectra. Recent progress in anharmonic quantum mechanical calculations allows for accurate reconstruction of NIR spectra. Taking this opportunity, we carried out a systematic study of NIR spectra of six isotopomers of ethanol (CX₃CX₂OX; X = H, D). Besides, we calculated the theoretical spectra of two other isotopomers (CH₃CD₂OD and CD₃CH₂OD) for which the experimental spectra are not available. The anharmonic calculations were based on generalized vibrational second-order perturbation theory (GVPT2) at DFT and MP2 levels with several basis sets. We compared the accuracy and efficiency of various computational methods. It appears that the best results were obtained with B2PLYP-GD3BJ/def2-TZVP//CPCM approach. Our simulations included the first and second overtones, as well as binary and ternary combinations bands. This way, we reliably reproduced even minor bands in the spectra of diluted samples (0.1 M in CCl₄). On this basis, the effect of isotopic substitution on NIR spectra of ethanol was accurately reproduced and comprehensively explained. Full article

Melamine (IUPAC: 1,3,5-Triazine-2,4,6-triamine) attracts high attention in analytical vibrational spectroscopy due to its misuse as a food adulterant. Vibrational spectroscopy [infrared (IR) and Raman and near-infrared (NIR) spectroscopy] is a major quality control tool in the detection and quantification of melamine content. The physical background for the measured spectra is not interpreted in analytical spectroscopy using chemometrics. In contrast, quantum mechanical calculations are capable of providing deep and independent insights therein. So far, the NIR region of crystalline melamine has not been studied by quantum mechanical calculations, while the investigations of its IR spectra have remained limited. In the present work, we employed fully anharmonic calculation of the NIR spectrum of melamine based on finite models, and also performed IR spectral simulation by using an infinite crystal model—periodic in three dimensions. This yielded detailed and unambiguous NIR band assignments and revised the previously known IR band assignments. We found that the out-of-plane fundamental transitions, which are essential in the IR region, are markedly more sensitive to out-of-plane inter-molecular interactions of melamine than NIR transitions. Proper description of the chemical surrounding of the molecule of melamine is more important than the anharmonicity of its vibrations. In contrast, the NIR bands mostly arise from in-plane vibrations, and remain surprisingly insensitive to the chemical environment. These findings explain previous observations that were reported in IR and NIR analytical studies of melamine. Full article

The absorption properties of Temoporfin, a second-generation photosensitizer employed in photodynamic therapy, are calculated with an electrostatic-embedding quantum mechanics/molecular mechanics (QM/MM) scheme in methanol. The suitability of several ensembles of geometries generated by different sampling techniques, namely classical-molecular-dynamics (MD) and QM/MM-MD thermal sampling, Wigner quantum sampling and a hybrid protocol, which combines the thermal and quantum approaches, is assessed. It is found that a QM description of the chromophore during the sampling is needed in order to achieve a good agreement with respect to the experimental spectrum. Such a good agreement is obtained with both QM/MM-MD and Wigner samplings, demonstrating that a proper description of the anharmonic motions of the chromophore is not relevant in the computation of the absorption properties. In addition, it is also found that solvent organization is a rather fast process and a long sampling is not required. Finally, it is also demonstrated that the same exchange-correlation functional should be employed in the sampling and in the computation of the excited states properties to avoid unphysical triplet states with relative energies close or below 0 eV. Full article

We review a theory that predicts the onset of thermalization in a quantum mechanical coupled non-linear oscillator system, which models the vibrational degrees of freedom of a molecule. A system of N non-linear oscillators perturbed by cubic anharmonic interactions exhibits a many-body localization (MBL) transition in the vibrational state space (VSS) of the molecule. This transition can occur at rather high energy in a sizable molecule because the density of states coupled by cubic anharmonic terms scales as N³, in marked contrast to the total density of states, which scales as exp(aN), where a is a constant. The emergence of a MBL transition in the VSS is seen by analysis of a random matrix ensemble that captures the locality of coupling in the VSS, referred to as local random matrix theory (LRMT). Upon introducing higher order anharmonicity, the location of the MBL transition of even a sizable molecule, such as an organic molecule with tens of atoms, still lies at an energy that may exceed the energy to surmount a barrier to reaction, such as a barrier to conformational change. Illustrative calculations are provided, and some recent work on the influence of thermalization on thermal conduction in molecular junctions is also discussed. Full article

A method is described to solve the nonlinear Langevin equations arising from quadratic interactions in quantum mechanics. While the zeroth order linearization approximation to the operators is normally used, here, first and second order truncation perturbation schemes are proposed. These schemes employ higher-order system operators, and then approximate number operators with their corresponding mean boson numbers only where needed. Spectral densities of higher-order operators are derived, and an expression for the second-order correlation function at zero time-delay has been found, which reveals that the cavity photon occupation of an ideal laser at threshold reaches $\sqrt{6}-2$ , in good agreement with extensive numerical calculations. As further applications, analysis of the quantum anharmonic oscillator, calculation of Q-functions, analysis of quantum limited amplifiers, and nondemoliton measurements are provided. Full article