Search results for "time-dependent density functional theory"
showing 10 items of 59 documents
Carbonyl-functionalized quaterthiophenes: a study of the vibrational Raman and electronic absorption/emission properties guided by theoretical calcul…
2011
This work investigates the evolution of the molecular, vibrational, and optical properties within a family of carbonyl-functionalized quaterthiophenes: 5,5'''-diheptanoyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'''-diperfluorohexylcarbonyl-2,2':5',2'':5'',2'''-quaterthiophene (2), and 2,7-[bis(5-perfluorohexylcarbonylthien-2-yl)]-4H-cyclopenta[2,1-b:3,4-b']-dithiophene-4-one (3). The analysis is performed by Raman and UV/Vis absorption/excitation/fluorescence spectroscopy in combination with density functional calculations. Theoretical calculations show that substitution with carbonyl groups and perfluorohexyl chains induces progressive quinoidization of the π-conjugated backbone in co…
The first example of cofacial bis(dipyrrins)
2016
International audience; Two series of cofacial bis(dipyrrins) were prepared and their photophysical properties as well as their bimolecular fluorescence quenching with C-60 were investigated. DFT and TDDFT computations were also performed as a modeling tool to address the nature of the fluorescence state and the possible inter-chromophore interactions. Clearly, there is no evidence for such interactions and the bimolecular quenching of fluorescence, in comparison with mono-dipyrrins, indicates that C-60-bis(dipyrrin) contacts occur from the outside of the "mouth" of the cofacial structure.
Ab initio angle- and energy-resolved photoelectron spectroscopy with time-dependent density-functional theory
2012
We present a time-dependent density-functional method able to describe the photoelectron spectrum of atoms and molecules when excited by laser pulses. This computationally feasible scheme is based on a geometrical partitioning that efficiently gives access to photoelectron spectroscopy in time-dependent density-functional calculations. By using a geometrical approach, we provide a simple description of momentum-resolved photoemission including multiphoton effects. The approach is validated by comparison with results in the literature and exact calculations. Furthermore, we present numerical photoelectron angular distributions for randomly oriented nitrogen molecules in a short near-infrared…
Unraveling materials Berry curvature and Chern numbers from real-time evolution of Bloch states
2019
Materials can be classified by the topological character of their electronic structure and, in this perspective, global attributes immune to local deformations have been discussed in terms of Berry curvature and Chern numbers. Except for instructional simple models, linear response theories have been ubiquitously employed in calculations of topological properties of real materials. Here we propose a completely different and versatile approach to get the topological characteristics of materials by calculating physical observables from the real-time evolving Bloch states: the cell-averaged current density reveals the anomalous velocities whose integration leads to the conductivity quantum. Re…
Radical cations and dications of bis[1]benzothieno[1,4]thiazine isomers
2021
Bis[1]benzothieno[1,4]thiazines (BBTT) are particularly electron-rich S,N-heteropentacenes and their radical cations and dications can be relevant intermediates in charge transport materials. All three regioisomers of N-p-fluorophenyl-BBTT (syn–syn, syn–anti, and anti–anti) were studied. A reliable preparation of radical cations and dications using antimony pentachloride as an oxidant gives deeply colored salts. The electronic structure of the radical cations was assessed by EPR spectroscopy, whereas dicationic structures were characterized by NMR spectroscopy. In addition, a deeper insight into the electronic structure was experimentally and computationally obtained by UV/Vis spectroscopy …
Assignment of Configuration in a Series of Dioxolanone-Type Secondary Metabolites fromGuignardia bidwellii- A Comparison of VCD and ECD Spectroscopy
2013
The absolute configurations of a series of phytotoxic dioxolanone-type secondary metabolites isolated from culture filtrates of the grape black rot fungus Guignardia bidwellii were determined by vibrational circular dichroism (VCD) spectroscopy in the mid-IR frequency range. Comparison of the recorded data with DFT calculations showed good agreement between experiment and theory for VCD, whereas electronic circular dichroism (ECD) data for the compounds matched poorly with the predicted spectra obtained by time-dependent DFT (TDDFT) calculations at the same level of theory.
New Austalides from the Sponge-Associated Fungus Aspergillus sp.
2011
Chromatographic separation of a crude extract obtained from the fungus Aspergillus sp., isolated from the Mediterranean sponge Tethya aurantium, yielded five new meroterpenoid metabolites, austalides M–Q (1–5), together with nine known compounds (6–13). The structures of the new compounds were unambiguously elucidated on the basis of extensive 1D and 2D NMR methods and by mass spectral analysis. Furthermore, the absolute configurations of 1 and 4 were determined by time-dependent density functional theory electronic circular dichroism (TDDFT ECD) calculations, allowing the assignment of the absolute configuration of analogous compounds 2, 3, and 5. The calculations revealed that the conform…
Existence, uniqueness, and construction of the density-potential mapping in time-dependent density-functional theory
2014
In this work we review the mapping from densities to potentials in quantum mechanics, which is the basic building block of time-dependent density-functional theory and the Kohn-Sham construction. We first present detailed conditions such that a mapping from potentials to densities is defined by solving the time-dependent Schr\"odinger equation. We specifically discuss intricacies connected with the unboundedness of the Hamiltonian and derive the local-force equation. This equation is then used to set up an iterative sequence that determines a potential that generates a specified density via time propagation of an initial state. This fixed-point procedure needs the invertibility of a certain…
Response calculations based on an independent particle system with the exact one-particle density matrix: Excitation energies
2012
Adiabatic response time-dependent density functional theory (TDDFT) suffers from the restriction to basically an occupied → virtual single excitation formulation. Adiabatic time-dependent density matrix functional theory allows to break away from this restriction. Problematic excitations for TDDFT, viz. bonding-antibonding, double, charge transfer, and higher excitations, are calculated along the bond-dissociation coordinate of the prototype molecules H2 and HeH+ using the recently developed adiabatic linear response phase-including (PI) natural orbital theory (PINO). The possibility to systematically increase the scope of the calculation from excitations out of (strongly) occupied into wea…
Oscillator Strengths of Electronic Excitations with Response Theory using Phase Including Natural Orbital Functionals
2013
The key characteristics of electronic excitations of many-electron systems, the excitation energies ωα and the oscillator strengths fα, can be obtained from linear response theory. In one-electron models and within the adiabatic approximation, the zeros of the inverse response matrix, which occur at the excitation energies, can be obtained from a simple diagonalization. Particular cases are the eigenvalue equations of time-dependent density functional theory (TDDFT), time-dependent density matrix functional theory, and the recently developed phase-including natural orbital (PINO) functional theory. In this paper, an expression for the oscillator strengths fα of the electronic excitations is…