Search results for "PERTURBATION"
showing 10 items of 811 documents
Redox potentials and acidity constants from density functional theory based molecular dynamics.
2014
CONSPECTUS: All-atom methods treat solute and solvent at the same level of electronic structure theory and statistical mechanics. All-atom computation of acidity constants (pKa) and redox potentials is still a challenge. In this Account, we review such a method combining density functional theory based molecular dynamics (DFTMD) and free energy perturbation (FEP) methods. The key computational tool is a FEP based method for reversible insertion of a proton or electron in a periodic DFTMD model system. The free energy of insertion (work function) is computed by thermodynamic integration of vertical energy gaps obtained from total energy differences. The problem of the loss of a physical refe…
Modeling21Ne NMR parameters for carbon nanosystems
2013
The potential of nuclear magnetic resonance (NMR) technique in probing the structure of porous systems including carbon nanostructures filled with inert gases is analysed theoretically using accurate calculations of neon ((21) Ne) nuclear magnetic shieldings. The CBS estimates of (21) Ne NMR parameters were performed for single atom, its dimer and neon interacting with acetylene, ethylene and 1,3-cyclopentadiene. Several levels of theory including restricted Hartree-Fock (RHF), Moller-Plesset perturbation theory to the second order (MP2), density functional theory (DFT) with van Voorhis and Scuseria's t-dependent gradient-corrected correlation functional (VSXC), coupled cluster with single …
PT-symmetry and Schrödinger operators. The double well case
2015
We study a class of $PT$-symmetric semiclassical Schrodinger operators, which are perturbations of a selfadjoint one. Here, we treat the case where the unperturbed operator has a double-well potential. In the simple well case, two of the authors have proved in [6] that, when the potential is analytic, the eigenvalues stay real for a perturbation of size $O(1)$. We show here, in the double-well case, that the eigenvalues stay real only for exponentially small perturbations, then bifurcate into the complex domain when the perturbation increases and we get precise asymptotic expansions. The proof uses complex WKB-analysis, leading to a fairly explicit quantization condition.
A method for the investigation of high-order two-frequency asynchronous oscillators
1992
A general method for analysing asynchronous high-order two-frequency oscillators is presented. the oscillator model is made up of a GC non-linear parallel group embedded in a linear lumped time-invariant network of any order. the approach devised rests on the identification of a pair of narrow-band impedance operators which permit one to derive first-approximation steady state and dynamic equations in the phasor domain—as well as stability criteria—in a simple and expressive manner. Previous results from averaging and perturbation treatments on fourth-order asynchronous oscillators are shown to be obtainable from this theory as particular cases. the sixth-order oscillator chosen as an appli…
Disorder-induced single-mode transmission.
2017
Localized states trap waves propagating in a disordered potential and play a crucial role in Anderson localization, which is the absence of diffusion due to disorder. Some localized states are barely coupled with neighbours because of differences in wavelength or small spatial overlap, thus preventing energy leakage to the surroundings. This is the same degree of isolation found in the homogeneous core of a single-mode optical fibre. Here we show that localized states of a disordered optical fibre are single mode: the transmission channels possess a high degree of resilience to perturbation and invariance with respect to the launch conditions. Our experimental approach allows identification…
An orbital floating time scale of the Hauterivian/Barremian GSSP from a magnetic susceptibility signal (Río Argos, Spain).
2012
10 pages; International audience; An orbital floating time scale of the HauterivianeBarremian transition (Early Cretaceous) is proposed using high-resolution magnetic susceptibility measurements. Orbital tuning was performed on the Río Argos section (southeast Spain), the candidate for a Global boundary Stratotype Section and Point (GSSP) for the HauterivianeBarremian transition. Spectral analyses of MS variations, coupled with the frequency ratio method, allow the recognition of precession, obliquity and eccentricity frequency bands. Orbitallytuned magnetic susceptibility provides minimum durations for ammonite biozones. The durations of well-constrained ammonite zones are assessed at 0.78…
Approximate energy functionals for one-body reduced density matrix functional theory from many-body perturbation theory
2018
We develop a systematic approach to construct energy functionals of the one-particle reduced density matrix (1RDM) for equilibrium systems at finite temperature. The starting point of our formulation is the grand potential $\Omega [\mathbf{G}]$ regarded as variational functional of the Green's function $G$ based on diagrammatic many-body perturbation theory and for which we consider either the Klein or Luttinger-Ward form. By restricting the input Green's function to be one-to-one related to a set on one-particle reduced density matrices (1RDM) this functional becomes a functional of the 1RDM. To establish the one-to-one mapping we use that, at any finite temperature and for a given 1RDM $\…
Ab initio determination of the electron affinities of DNA and RNA nucleobases
2008
High-level quantum-chemical ab initio coupled-cluster and multiconfigurational perturbation methods have been used to compute the vertical and adiabatic electron affinities of the five canonical DNA and RNA nucleobases: uracil, thymine, cytosine, adenine, and guanine. The present results aim for the accurate determination of the intrinsic electron acceptor properties of the isolated nucleic acid bases as described by their electron affinities, establishing an overall set of theoretical reference values at a level not reported before and helping to rule out less reliable theoretical and experimental data and to calibrate theoretical strategies. Daniel.Roca@uv.es Manuela.Merchan@uv.es Luis.Se…
First-principles characterization of the singlet excited state manifold in DNA/RNA nucleobases
2020
An extensive theoretical characterization of the singlet excited state manifold of the five canonical DNA/RNA nucleobases (thymine, cytosine, uracil, adenine and guanine) in gas-phase is carried out with time-dependent density functional theory (TD-DFT) and restricted active space second-order perturbation theory (RASPT2) approaches. Both ground state and excited state absorptions are analyzed and compared between these different theoretical approaches, assessing the performance of the hybrid B3LYP and CAM-B3LYP (long-range corrected) functionals with respect to the RASPT2 reference. By comparing the TD-DFT estimates with our reference for high-lying excited states, we are able to narrow do…
Dosimetric perturbations of a lead shield for surface and interstitial high-dose-rate brachytherapy.
2014
In surface and interstitial high-dose-rate brachytherapy with either (60)Co, (192)Ir, or (169)Yb sources, some radiosensitive organs near the surface may be exposed to high absorbed doses. This may be reduced by covering the implants with a lead shield on the body surface, which results in dosimetric perturbations. Monte Carlo simulations in Geant4 were performed for the three radionuclides placed at a single dwell position. Four different shield thicknesses (0, 3, 6, and 10 mm) and three different source depths (0, 5, and 10 mm) in water were considered, with the lead shield placed at the phantom surface. Backscatter dose enhancement and transmission data were obtained for the lead shields…