Search results for " orbita"
showing 10 items of 447 documents
Efficient Green Light-Emitting Electrochemical Cells Based on Ionic Iridium Complexes with Sulfone-Containing Cyclometalating Ligands
2013
A new approach to obtain green-emitting iridiumA complexes is described. The synthetic approach consists of introducing a methylsulfone electron-withdrawing substituent into a 4-phenylpyrazole cyclometalating ligand in order to stabilize the highest- occupied molecular orbital (HOMO). Six new complexes have been synthe- sized incorporating the conjugate base of 1-(4-(methylsulfonyl)phenyl)-1 H- pyrazole as the cyclometalating ligand. The complexes show green emission and very high photoluminescence quantum yields in both diluted and concentrated films. When used as the main active component in light-emit- ting electrochemical cells (LECs), green electroluminance is observed. High efficienci…
Ultrafast Electron Transfer in Photosynthesis: Reduced Pheophytin and Quinone Interaction Mediated by Conical Intersections
2007
The mechanism of electron transfer (ET) from reduced pheophytin (Pheo−) to the primary stable photosynthetic acceptor, a quinone (Q) molecule, is addressed by using high‐level ab initio computations and realistic molecular models. The results reveal that the ET process involving the (Pheo−+Q) and (Pheo+Q−) oxidation states can be essentially seen as an ultrafast radiationless transition between the two hypersurfaces taking place via conical intersections (CIs) and it is favoured when the topology of the interacting moieties make possible some overlap between the lowest occupied molecular orbitals (LUMO) of the two systems. Thus, it is anticipated that large scale motions, which are difficul…
Transition-Dipole Moments for Electronic Excitations in Strong Magnetic Fields Using Equation-of-Motion and Linear Response Coupled-Cluster Theory
2019
An implementation of transition-dipole moments at the equation-of-motion coupled-cluster singles-doubles (EOM-CCSD) and CCSD linear response (LR) levels of theory for the treatment of atoms and molecules in strong magnetic fields is presented. The presence of a finite magnetic field leads, in general, to a complex wave function and a gauge-origin dependence, necessitating a complex computer code together with the use of gauge-including atomic orbitals. As in the field-free case, for EOM-CC, the evaluation of transition-dipole moments consists of setting up the one-electron transition-density matrix (TDM) which is then contracted with dipole-moment integrals. In the case of CC-LR, the evalua…
Equation-of-motion coupled-cluster methods for atoms and molecules in strong magnetic fields.
2017
A program for the direct calculation of excitation energies of atoms and molecules in strong magnetic fields is presented. The implementation includes the equation-of-motion coupled-cluster singles-doubles (EOM-CCSD) method for electronically excited states as well as its spin-flip variant. Differences to regular EOM-CCSD implementations are due to the appearance of the canonical angular-momentum operator in the Hamiltonian causing the wave function to become complex. The gauge-origin problem is treated by the use of gauge-including atomic orbitals. Therefore, a modified Davidson method for diagonalizing complex non-Hermitian matrices is used. Excitation energies for selected atoms and mole…
DLPNO-MP2 second derivatives for the computation of polarizabilities and NMR shieldings
2021
We present a derivation and efficient implementation of the formally complete analytic second derivatives for the domain-based local pair natural orbital second order Møller–Plesset perturbation theory (MP2) method, applicable to electric or magnetic field-response properties but not yet to harmonic frequencies. We also discuss the occurrence and avoidance of numerical instability issues related to singular linear equation systems and near linear dependences in the projected atomic orbital domains. A series of benchmark calculations on medium-sized systems is performed to assess the effect of the local approximation on calculated nuclear magnetic resonance shieldings and the static dipole …
Shell-Structure and Pairing Interaction in Superheavy Nuclei: Rotational Properties of theZ=104NucleusRf256
2012
The rotational band structure of the $Z=104$ nucleus $^{256}\mathrm{Rf}$ has been observed up to a tentative spin of $20\ensuremath{\hbar}$ using state-of-the-art $\ensuremath{\gamma}$-ray spectroscopic techniques. This represents the first such measurement in a superheavy nucleus whose stability is entirely derived from the shell-correction energy. The observed rotational properties are compared to those of neighboring nuclei and it is shown that the kinematic and dynamic moments of inertia are sensitive to the underlying single-particle shell structure and the specific location of high-$j$ orbitals. The moments of inertia therefore provide a sensitive test of shell structure and pairing i…
Highly deformed bands in Nd nuclei: New results and consistent interpretation within the cranked Nilsson-Strutinsky formalism
2019
International audience; Three new highly-deformed (HD) bands are identified in Nd136 and the highly deformed band of Nd137 is extended at higher spin by four transitions, revealing a band crossing associated with the occupation of the second νi13/2 intruder orbital. Extended cranked Nilsson-Strutinsky calculations are performed for all HD bands observed in Nd134, Nd136, and Nd137, achieving for the first time a consistent interpretation of all HD bands in the Nd nuclei. The new interpretation has significant consequences, like the change of parity of the yrast HD bands of Nd134 and Nd136, and the involvement of two negative-parity neutron intruder orbitals in the configurations of most HD b…
Occupation Number Representation
2007
The first two chapters of this book presented angular momentum algebra as the basic tool of nuclear theory. That includes angular momentum coupling coefficients, spherical tensor operators and reduced matrix elements. In the preceding chapter we introduced the mean-field concept, along with associated many-nucleon wave functions, Slater determinants, describing configurations of non-interacting particles in mean-field single-particle orbitals.
Theoretical study of the electron structure of superheavy elements with an open 6d shell: Sg, Bh, Hs, and Mt
2019
We use recently developed efficient versions of the configuration interaction method to perform {\em ab initio} calculations of the spectra of superheavy elements seaborgium (Sg, $Z=106$), bohrium (Bh, $Z=107$), hassium (Hs, $Z=108$) and meitnerium (Mt, $Z=109$). We calculate energy levels, ionization potentials, isotope shifts and electric dipole transition amplitudes. Comparison with lighter analogs reveals significant differences caused by strong relativistic effects in superheavy elements. Very large spin-orbit interaction distinguishes subshells containing orbitals with a definite total electron angular momentum $j$. This effect replaces Hund's rule holding for lighter elements.
Spin-multipole nuclear matrix elements in thepnquasiparticle random-phase approximation: Implications forβandββhalf-lives
2017
Half-lives for 148 potentially measurable 2nd-, 3rd-, 4th-, 5th-, 6th-, and 7th-forbidden unique beta transitions are predicted. To achieve this, the ratio of the nuclear matrix elements (NMEs), calculated by the proton-neutron quasiparticle random-phase approximation (pnQRPA), ${M}_{\mathrm{pnQRPA}}$, and a two-quasiparticle (two-qp) model, ${M}_{\mathrm{qp}}$, is studied and compared with earlier calculations for the allowed Gamow-Teller (GT) ${1}^{+}$ and first-forbidden spin-dipole (SD) ${2}^{\ensuremath{-}}$ transitions. The present calculations are done using realistic single-particle model spaces and $G$-matrix based microscopic two-body interactions. In terms of the ratio $k={M}_{\m…