Search results for "Ground State"
showing 10 items of 928 documents
Specific orientation of dipole moments in azocrown cetocyanine dyes determined by electrooptical absorption measurements (EOAM)
2019
Abstract From electrooptical absorption measurements (EOAM) follows that the dipole moments of azacrown ketocyanine dyes 2,5-di{(E)-1-[4-(4,7,10,13-tetraoxa-1-azacyclopentadecyl)phenyl]methylidene}-1-cyclopentanone (Compound 1) and (E)-1-(2-hydroxy-4methoxyphenyl)-3-[4-(4,7,10,13-tetraoxa-1-azacyclopentadecyl)phenyl]-2-propen-1-one (Compound 2) in the equilibrium ground state μg and the change of dipole moments upon transition to the excited Franck–Condon state Δaμ are large. This alteration causes a significant long-wavelength shift of the absorption and emission spectra, as well as large fluorescence Stokes shift with increasing polarity of the solvent. From the DFT calculations follows t…
Axialisation, cooling and quenching of $\mathsf{Ba^+}$ ions in a Penning trap
1998
Collisions of ions, stored in a Penning trap, with neutral background molecules usually lead to rapid ion loss from the trap unless the ions are excited by the sum of the frequencies of the reduced cyclotron and magnetron motion. Then the ions are cooled by collisions and are driven to the trap centre leading to substantial increase of the storage time. Furthermore in a three level system including a long living metastable state collisions deexcite this metastable state and increase the population density in the ionic ground state. In a laser spectroscopic experiment we demonstrate the advantages of collisions on Ba+ ions stored in a Penning trap. The combined action of metastable state que…
Diagonalization of large matrices: a new parallel algorithm.
2015
On the basis of a dressed matrices formalism, a new algorithm has been devised for obtaining the lowest eigenvalue and the corresponding eigenvector of large real symmetric matrices. Given an N × N matrix, the proposed algorithm consists in the diagonalization of (N - 1)2 × 2 dressed matrices. Both sequential and parallel versions of the proposed algorithm have been implemented. Tests have been performed on a Hilbert matrix, and the results show that this algorithm is up 340 times faster than the corresponding LAPACK routine for N = 10(4) and about 10% faster than the Davidson method. The parallel MPI version has been tested using up to 512 nodes. The speed-up for a N = 10(6) matrix is fair…
Exchange transfer in high-nuclearity mixed valence magnetic clusters: Theoretical approach and expected manifestations
1998
Abstract We report here a general solution of the exchange transfer problem in the high-nuclearity mixed valence clusters containing arbitrary number of itinerant electrons. The concept of two kinds of exchange transfer, namely kinetic and potential, is introduced by analogy with basic Anderson's mechanisms of the magnetic exchange. The kinetic exchange transfer is treated as a second order transfer process between two centres through the excited state of a third centre. The potential exchange transfer is also considered as a three-centre interaction but in this case only the ground states of the constituent ions are involved. The actual parameters of the exchange transfer are expected to b…
Energy and entropy barriers of two-level systems in argon clusters: An energy landscape approach
1999
Abstract Free argon clusters containing up to 160 atoms have been studied by means of a numerical algorithm for finding thousands of adjacent minima connected through a first-order saddle point. Many minimum-saddle-minimum systems have been found to be good candidates for forming two-level systems. The ground state splitting has been evaluated by taking into account both energy and entropy barriers. The role of the latter in auenching or enhancing the ground state splitting is discussed with the aid of a simple model potential.
Crystal and molecular structure, and electronic properties of hexakis(imidazole)copper(II) formate
1996
The crystal and molecular structure of [Cu(Im)6] (HCOO)2 (Im = imidazole) has been determined by X-ray diffraction methods. The compound is built of centrosymmetric Cu(Im) inf6 sup2− cations and non-coordinated HCO2 − anions, linked through H-bonds giving a layered structure in the ac plane. The coordination polyhedron around the Cu atoms can be described as a rhombically-distorted octahedron (CuN2N′2N′'2 chromophores). Both electronic and e.p.r. spectra are indicative of an essentially d x2− y2 ground state for the CuII ions. No exchange coupling has been detected down to 4.2 K by means of magnetic susceptibility measurements. This feature is discussed on the basis of the structural data.
Photoinduced Formation Mechanism of the Thymine−Thymine (6−4) Adduct
2013
The photoinduced mechanism leading to the formation of the thymine-thymine (6-4) photolesion has been studied by using the CASPT2//CASSCF approach over a dinucleotide model in vacuo. Following light absorption, localization of the excitation on a single thymine leads to fast singlet-triplet crossing that populates the triplet (3)(nπ*) state of thymine. This state, displaying an elongated C(4)═O bond, triggers (6-4) dimer formation by reaction with the C(5)═C(6) double bond of the adjacent thymine, followed by a second intersystem crossing, which acts as a gate between the excited state of the reactant and the ground state of the photoproduct. The requirement of localized excitation on just …
Structural and magnetic characterization of a 1D chain of [Co(II)2(mu-aqua)(mu-carboxylate)2] strung cores.
2009
A novel 1D chain built up from stringing of [Co2(μ-OH 2)(μ-O2CC(CH3)3)2] units with the bridging 2,2′-bipyrimidine ligand has been synthesized and structurally characterized. The chains are well isolated from each other by the bulky tert-butyl groups of the carboxlyates and show an alternating zigzag configuration for the Co(II) metallic centres. DC magnetic measurements show anti-ferromagnetic coupling, Jca.-3 cm-1 between adjacent Co(II) ions along the chain. Noticeably, good data fitting was obtained by means of simple models that neglect any kind of first order orbital contribution to the spin ground state, which is normally observed in Co(II) complexes. These results were further confi…
The Role of Adenine Excimers in the Photophysics of Oligonucleotides
2009
Energies and structures of different arrangements of the stacked adenine homodimer have been computed at the ab initio CASPT2 level of theory in isolation and in an aqueous environment. Adenine dimers are shown to form excimer singlet states with different degrees of stacking and interaction. A model for a 2-fold decay dynamics of adenine oligomers can be supported in which, after initial excitation in the middle UV range, unstacked or slightly stacked pairs of nucleobases will relax by an ultrafast internal conversion to the ground state, localizing the excitation in the monomer and through the corresponding conical intersection with the ground state. On the other hand, long-lifetime intra…
Effect of temperature and ligand protonation on the electronic ground state in Cu( ii ) polymers having unusual secondary interactions: a magnetic an…
2018
International audience; Two new copper(II) polymeric complexes, {[Cu(HPymat)(H2O)](NO3)}n (1) and [Cu2(Pymat)2(H2O)3]n (2), have been synthesized using the Schiff base ligand H2Pymat [H2Pymat = (E)-2-(1-(pyridin-2-yl)-methyleneamino)terephthalic acid]. Complex 1 is a cationic 1D polymer, whereas complex 2 is a two dimensional polymer. Both complexes were crystallographically, spectroscopically and magnetically characterized. Theoretical studies were performed and the catecholase activity of the complexes was also examined. Complex 1 is a ferromagnetically coupled complex with J = 2.8 cm−1 and 2 shows antiferromagnetic coupling with J = −1.6 cm−1. Both complexes show notable features in the …