*J Phys Condens Matter ; 33(7): 075201, 2021 Feb 17.*

##### RESUMO

Our calculations of the excitation spectrum of single-layer MoS2 at several hydrogen coverages, using a density-matrix based time-dependent density-functional theory (TDDFT) show that the fully hydrogenated system is metallic, while at lower coverages the spectrum consists of spin-polarized partially filled localized mid-gap states. The calculated absorption spectrum of the system reveals standard excitonic peaks corresponding to the bound valence-band hole and conduction-band electron, as well as excitonic peaks that involve the mid-gap states. Binding energies of the excitons of the hydrogenated system are found to be relatively large (few tens of meV), making their experimental detection facile and suggesting hydrogenation as a knob for tuning the optical properties of single-layer MoS2. Importantly, we find hydrogenation to suppress visible light photoluminescence, in agreement with experimental observations. In contrast, both Li and Na atoms transform the system into an n-doped non-magnetic semiconductor that does not allow excitonic states.

*J Phys Condens Matter ; 2020 Jul 29.*

##### RESUMO

To analyze the role of electron-electron correlation effects in structural (local-geometry), spectral and polarization properties of tetragonal BaTiO3 we apply DFT+U approach. We demonstrate that the system properties drastically change when the value of the local Coulomb repulsion U crosses the critical value U_c ≈ 7 eV. In particular, the correlation effects cause a change of the ratio of the in-plane and inter-plane Ti-O bond lengths, which results in a flip of the order of the Ti d-bands and change of the polarizability of the system. Since the exact value of U in BaTiO3 is unknown, we discuss how the obtained results may be revealed in experimental data, especially in the optical response and ultrafast charge dynamics, where effective U is dynamically tuned.

*Phys Rev Lett ; 125(1): 017202, 2020 Jul 03.*

##### RESUMO

Experimental observations of the ultrafast (less than 50 fs) demagnetization of Ni have so far defied theoretical explanations particularly since its spin-flipping time is much less than that resulting from spin-orbit and electron-lattice interactions. Through the application of an approach that benefits from spin-flip time-dependent density-functional theory and dynamical mean-field theory, we show that proper inclusion of electron correlations and memory (time dependence of electron-electron interaction) effects leads to demagnetization at the femtosecond scale, in good agreement with experimental observations. Furthermore, our calculations reveal that this ultrafast demagnetization results mainly from spin-flip transitions from occupied to unoccupied orbitals implying a dynamical reduction of exchange splitting. These conclusions are found to be valid for a wide range of laser pulse amplitudes. They also pave the way for ab initio investigations of ultrafast charge and spin dynamics in a variety of quantum materials in which electron correlations may play a definitive role.

*J Phys Condens Matter ; 32(20): 20LT01, 2020 May 13.*

##### RESUMO

By applying an approach based on time-dependent density functional theory and dynamical mean-field theory (TDDFT+DMFT) we examine the role of electron correlations in the ultrafast breakdown of the insulating M1 phase in bulk VO2. We consider the case of a spatially homogeneous ultrafast (femtosecond) laser pulse perturbation and present the dynamics of the melting of the insulating state, in particular the time-dependence of the excited charge density. The time-dependence of the chemical potential of the excited electron and hole subsystems shows that even for such short times the dynamics of the system is significantly affected by memory effects-the time-resolved electron-electron interactions. The results pave the way for obtaining a microscopic understanding of the ultrafast dynamics of strongly-correlated materials.

*ACS Nano ; 13(5): 5344-5355, 2019 May 28.*

##### RESUMO

Features of the surface plasmon from macroscopic materials emerge in molecular systems, but differentiating collective excitations from single-particle excitations in molecular systems remains elusive. The rich interactions between single-particle electron-hole and collective electron excitations produce phenomena related to the chemical physics aspects within the atomic array. We study the plasmonic properties of atomic arrays of noble (Au, Ag, and Cu) and transition-metal (Pd, Pt) homonuclear chains using time-dependent density functional theory and their Kohn-Sham transition contributions. The response to the electromagnetic radiation is related to both the geometry-dependent confinement of sp-valence electrons and the energy position of d-electrons in the different atomic species and the hybridization between d and sp electrons. It is possible to tune the position of the plasmon resonance, split it into several peaks, and eventually achieve broadband absorption of radiation. Arrays of mixed noble and transition-metal chains may have strongly attenuated plasmonic behavior. The collective nature of the excitations is ascertained using their Kohn-Sham transition contributions. To manipulate the plasmonic response and achieve the desired properties for broad applications, it is vital to understand the origins of these phenomena in atomic chains and their arrays.

*Nat Commun ; 9(1): 3720, 2018 09 13.*

##### RESUMO

We present time-integrated four-wave mixing measurements on monolayer MoSe2 in magnetic fields up to 25 T. The experimental data together with time-dependent density function theory calculations provide interesting insights into the biexciton formation and dynamics. In the presence of magnetic fields the coherence at negative and positive time delays is dominated by intervalley biexcitons. We demonstrate that magnetic fields can serve as a control to enhance the biexciton formation and help search for more exotic states of matter, including the creation of multiple exciton complexes and excitonic condensates.

*Chemphyschem ; 19(3): 277-283, 2018 Feb 05.*

##### RESUMO

Electroluminescence spectroscopy of organic semiconductors in the junction of a scanning tunneling microscope (STM) provides access to the polarizability of neutral excited states in a well-characterized molecular geometry. We study the Stark shift of the self-trapped lowest singlet exciton at 1.6â eV in a pentacene nanocrystal. Combination of density functional theory (DFT) and time-dependent DFT (TDDFT) with experiment allows for assignment of the observation to a charge-transfer (CT) exciton. Its charge separation is perpendicular to the applied field, as the measured polarizability is moderate and the electric field in the STM junction is strong enough to dissociate a CT exciton polarized parallel to the applied field. The calculated electric-field-induced anisotropy of the exciton potential energy surface will also be of relevance to photovoltaic applications.

*J Phys Condens Matter ; 29(45): 455601, 2017 Nov 15.*

##### RESUMO

We formulate a rigorous method for calculating a nonadiabatic (frequency-dependent) exchange-correlation (XC) kernel appropriate for accurate description of both equilibrium and nonequilibrium properties of strongly correlated systems within the time-dependent density functional theory (TDDFT) via the charge susceptibility, which is in turn obtained from dynamical mean field theory (DMFT) based on the effective multi-orbital Hubbard model. Application to the simple case of the one-orbital Hubbard model already shows the importance of the nonadiabatic kernel as it leads to significant modification of the excitation spectrum-shifting the (adiabatic) peak and disclosing another that is reminiscent of the solution from DMFT. The impact of dynamical effects, naturally included through the nonadiabaticity of the XC kernel, becomes even more transparent in our consideration of the nonequilibrium charge-density response of a multi-orbital perovskite, YTiO3, to a perturbation by a femtosecond (fs) laser pulse. These initial results indicate that electron-electron correlations and nonadiabatic features may significantly affect the spectrum and nonequilibrium properties of strongly correlated systems. We also propose an algorithm for extension of the approach to non-linear response. The transparency and computational efficiency of this non-adiabatic TDDFT+DMFT approach opens the door to examination of the spectra and response of multi-orbital systems with many nonequivalent atoms-bulk material, films and nanostructures.

*Opt Express ; 24(2): 1154-64, 2016 Jan 25.*

##### RESUMO

Nanoscale plasmonic phenomena observed in single and bi-layers of molybdenum disulfide (MoS(2)) on silicon dioxide (SiO(2)) are reported. A scattering type scanning near-field optical microscope (s-SNOM) with a broadband synchrotron radiation (SR) infrared source was used. We also present complementary optical mapping using tunable CO(2)-laser radiation. Specifically, there is a correlation of the topography of well-defined MoS(2) islands grown by chemical vapor deposition, as determined by atomic force microscopy, with the infrared (IR) signature of MoS(2). The influence of MoS(2) islands on the SiO(2) phonon resonance is discussed. The results reveal the plasmonic character of the MoS(2) structures and their interaction with the SiO(2) phonons leading to an enhancement of the hybridized surface plasmon-phonon mode. A theoretical analysis shows that, in the case of monolayer islands, the coupling of the MoS(2) optical plasmon mode to the SiO(2) surface phonons does not affect the infrared spectrum significantly. For two-layer MoS(2), the coupling of the extra inter-plane acoustic plasmon mode with the SiO(2) surface transverse phonon leads to a remarkable increase of the surface phonon peak at 794 cm(-1). This is in agreement with the experimental data. These results show the capability of the s-SNOM technique to study local multiple excitations in complex non-homogeneous structures.

*Opt Express ; 24(5): 4600, 2016 Mar 07.*

##### RESUMO

This publisher's note amends the Acknowledgments of a recent publication [Opt. Express24, 1154 (2016)10.1364/OE.24.001154].

*J Phys Condens Matter ; 27(12): 125601, 2015 Apr 01.*

##### RESUMO

For reliable and efficient inclusion of electron-electron correlation effects in nanosystems we formulate a combined density functional theory/nonhomogeneous dynamical mean-field theory (DFT+DMFT) approach which employs an approximate iterated perturbation theory impurity solver. We further apply the method to examine the size-dependent magnetic properties of iron nanoparticles containing 11-100 atoms. We show that for the majority of clusters the DFT+DMFT solution is in very good agreement with experimental data, much better compared to the DFT and DFT+U results. In particular, it reproduces the oscillations in magnetic moment with size as observed experimentally. We thus demonstrate that the DFT+DMFT approach can be used for accurate and realistic description of nanosystems containing about hundred atoms.

*J Phys Condens Matter ; 26(18): 185005, 2014 May 07.*

##### RESUMO

We have employed density functional theory, corrected by the on-site electron-electron repulsion energy U, to clarify the mechanism behind the enhanced orange photoluminescence (PL) of a CuI(1 1 1) thin film conjugated with a benzylpiperazine (BZP) molecule in the presence of an iodine 'vapor' atom. Our results demonstrated that the adsorbed molecule and the 'vapor' atom play complementary roles in producing the PL. The latter, in attaching to the film surface, creates a hole-trapping surface state located ~0.25 eV above the valence band-edge of the film, in good agreement with ~0.2 eV reported in experiments. Upon photo-excitation of the BZP/CuI(1 1 1) system in the presence of surface iodine 'vapor' atoms, excited electrons are transferred into the conduction band of CuI, and holes are trapped by the 'vapor' atoms. These holes, in turn, quickly relax into the HOMO state of the BZP molecule, owing to the fact that the molecule adsorbs on the film surface in the immediate vicinity of a 'vapor' atom. Relaxed holes subsequently recombine with excited electrons in the conduction band of the CuI film, thereby producing a luminescence peak at ~2.1 eV, in qualitative agreement with experimental findings.

##### Assuntos

Cobre/química , Iodetos/química , Iodo/química , Medições Luminescentes , Piperazinas/química , Adsorção , Modelos Moleculares , Conformação Molecular , Teoria Quântica , Propriedades de Superfície*J Phys Condens Matter ; 26(2): 022201, 2014 Jan 15.*

##### RESUMO

We propose a nonadiabatic time-dependent spin-density functional theory (TDSDFT) approach for studying single-electron excited states and the ultrafast response of systems with strong electron correlations. The correlation part of the nonadiabatic exchange-correlation (XC) kernel is constructed by using exact results for the Hubbard model of strongly correlated electrons. We demonstrate that the corresponding nonadiabatic XC kernel reproduces the main features of the spectrum of the Hubbard dimer and the 2D, 3D and infinite-dimensional Hubbard models, some of which are impossible to obtain within the adiabatic approach. The formalism may be applied for ab initio examination of strongly correlated electron systems in- and out-of-equilibrium within the TDSDFT, extending it beyond the metallic and semiconductor structures with plasmons, excitons and other excitations.

*Phys Rev Lett ; 109(15): 157404, 2012 Oct 12.*

##### RESUMO

Our examination of the optical properties of small gold chains containing up to 24 atoms doped with a transition metal (TM) atom (Ni, Rh, Fe), using the time-dependent density functional theory, show the splitting of the collective plasmon peak. We associate the additional peak with a local plasmonic mode which corresponds to charge oscillations around the potential created by the d orbitals of the impurity atoms. The effect is almost independent of the position of the TM atom in the chain, as long as it is not at the chain edge. This behavior is opposite to that of larger noble-metal-TM clusters (radius >1 nm), in which doping with TM atoms does not lead to generation of new modes, and often produces a suppression of the main plasmon peak.

*ACS Nano ; 6(6): 4854-63, 2012 Jun 26.*

##### RESUMO

Semiconductor nanoparticles conjugated with organic- and dye-molecules to yield high efficiency visible photoluminescence (PL) hold great potential for many future technological applications. We show that folic acid (FA)-conjugated to nanosize TiO(2) and CeO(2) particles demonstrates a dramatic increase of photoemission intensity at wavelengths between 500 and 700 nm when derivatized using aminopropyl trimethoxysilane (APTMS) as spacer-linker molecules between the metal oxide and FA. Using density-functional theory (DFT) and time-dependent DFT calculations we demonstrate that the strong increase of the PL can be explained by electronic transitions between the titania surface oxygen vacancy (OV) states and the low-energy excited states of the FA/APTMS molecule anchored onto the surface oxygen bridge sites in close proximity to the OVs. We suggest this scenario to be a universal feature for a wide class of metal oxide nanoparticles, including nanoceria, possessing a similar band gap (â¼3 eV) and with a large surface-vacancy-related density of electronic states. We demonstrate that the molecule-nanoparticle linker can play a crucial role in tuning the electronic and optical properties of nanosystems by bringing optically active parts of the molecule and of the surface close to each other.

##### Assuntos

Nanopartículas Metálicas/química , Nanopartículas Metálicas/ultraestrutura , Compostos Orgânicos/química , Óxidos/química , Cristalização/métodos , Luminescência , Teste de Materiais , Tamanho da Partícula , Propriedades de Superfície*J Chem Phys ; 136(11): 114108, 2012 Mar 21.*

##### RESUMO

Dynamical mean-field theory (DMFT) has established itself as a reliable and well-controlled approximation to study correlation effects in bulk solids and also two-dimensional systems. In combination with standard density-functional theory (DFT), it has been successfully applied to study materials in which localized electronic states play an important role. It was recently shown that this approach can also be successfully applied to study correlation effects in nanostructures. Here, we provide some details on our recently proposed DFT+DMFT approach to study the magnetic properties of nanosystems [V. Turkowski, A. Kabir, N. Nayyar, and T. S. Rahman, J. Phys.: Condens. Matter 22, 462202 (2010)] and apply it to examine the magnetic properties of small FePt clusters. We demonstrate that DMFT produces meaningful results even for such small systems. For benchmarking and better comparison with results obtained using DFT+U, we also include the case of small Fe clusters. As in the case of bulk systems, the latter approach tends to overestimate correlation effects in nanostructures. Finally, we discuss possible ways to further improve the nano-DFT+DMFT approximation and to extend its application to molecules and nanoparticles on substrates and to nonequilibrium phenomena.

##### Assuntos

Ligas/química , Nanopartículas de Magnetita/química , Simulação de Dinâmica Molecular , Ferro/química , Platina/química*Nano Lett ; 12(1): 518-21, 2012 Jan 11.*

##### RESUMO

The high intrinsic spin and long spin relaxation time of manganese-12-acetate (Mn(12)) makes it an archetypical single molecular magnet. While these characteristics have been measured on bulk samples, questions remain whether the magnetic properties replicate themselves in surface supported isolated molecules, a prerequisite for any application. Here we demonstrate that electrospray ion beam deposition facilitates grafting of intact Mn(12) molecules on metal as well as ultrathin insulating surfaces enabling submolecular resolution imaging by scanning tunneling microscopy. Using scanning tunneling spectroscopy we detect spin excitations from the magnetic ground state of the molecule at an ultrathin boron nitride decoupling layer. Our results are supported by density functional theory based calculations and establish that individual Mn(12) molecules retain their intrinsic spin on a well chosen solid support.

##### Assuntos

Acetatos/química , Imãs , Manganês/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Substâncias Macromoleculares/química , Campos Magnéticos , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de Superfície*J Phys Condens Matter ; 22(46): 462202, 2010 Nov 24.*

##### RESUMO

We propose a combined density-functional-theory-dynamical-mean-field-theory (DFT + DMFT) approach for reliable inclusion of electron-electron correlation effects in nanosystems. Compared with the widely used DFT + U approach, this method has several advantages, the most important of which is that it takes into account dynamical correlation effects. The formalism is illustrated through different calculations of the magnetic properties of a set of small iron clusters (number of atoms 2 ≤ N ≤ 5). It is shown that the inclusion of dynamical effects leads to a reduction in the cluster magnetization (as compared to results from DFT + U) and that, even for such small clusters, the magnetization values agree well with experimental estimations. These results justify confidence in the ability of the method to accurately describe the magnetic properties of clusters of interest to nanoscience.