Search results for "Ground state"
showing 8 items of 928 documents
.Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture
2020
International audience; A mononuclear iron(III) porphyrin compound exhibiting unexpectedly slow magnetic relaxation, which is a characteristic of single-ion magnet behaviour, is reported. This behaviour originates from the close proximity (approximate to 550 cm(-1)) of the intermediate-spinS=3/2 excited states to the high-spinS=5/2 ground state. More quantitatively, although the ground state is mostlyS=5/2, a spin-admixture model evidences a sizable contribution (approximate to 15 %) ofS=3/2 to the ground state, which as a consequence experiences large and positive axial anisotropy (D=+19.2 cm(-1)). Frequency-domain EPR spectroscopy allowed them(S)= |+/- 1/2⟩->|+/- 3/2&Rig…
The SO2F2 quasi-spherical top: Correspondence between tensorial and Watson's formalisms
2006
Abstract The SO2F2 quasi-spherical top molecule with C2v symmetry is considered as a distorted spherical top deriving from the SO 4 2 − tetrahedral ion. We present here a detailed correspondence between the tensorial formalism using the Td⊃C2v reorientation and the usual Hamiltonian of Watson. We have also performed ab initio calculations in order to determine the centrifugal distorsion constants in the vibrational ground state.
Comparison of the Richardson and BCS models of superconductivity based on calculations of ground state energies
2017
Suprajohtavuuden Richardsonin ja BCS mallien vertailu perustilojen laskettujen energioiden perusteella. Suprajohtavuus on edelleen aktiivinen tutkimuksen alue, koska sen tarjoamista mahdollisuuksista huolimatta sitä ei vielä ymmärretä kokonaisvaltaisesti. Tässä pro gradu -tutkielmassa käyn läpi perusteet kahdelle suprajohtavuuden mallille, Richardsonin ja BCS malleille. BCS teoria on ensimmäinen ja käytetyin mikroskooppinen suprajohtavuuden teoria. Richardsonin malli on harvemmin käytetty malli, josta saadaan redusoidun BCS Hamiltonin operaattorin tarkat ominaistilat. Lasken molempien mallien perustilojen energiat sekä redusoidulle että täydelle BCS Hamiltonin operaattorille. Sama lasketaan…
Impulsive excitation of high vibrational states in I2–Xe complex on the electronic ground state
2010
Abstract High vibrational states, up to ν = 22, are excited and investigated on the ground electronic state of a 1:1 I 2 –Xe complex isolated in solid Kr using femtosecond CARS technique and spontaneous resonant Raman measurements. The results show that this system is a promising candidate for investigations of coherent control of bimolecular reactions by using vibrational wavepackets on the ground electronic state.
Saddle index properties, singular topology, and its relation to thermodynamic singularities for aϕ4mean-field model
2004
We investigate the potential energy surface of a ${\ensuremath{\phi}}^{4}$ model with infinite range interactions. All stationary points can be uniquely characterized by three real numbers ${\ensuremath{\alpha}}_{+},{\ensuremath{\alpha}}_{0},{\ensuremath{\alpha}}_{\ensuremath{-}}$ with ${\ensuremath{\alpha}}_{+}+{\ensuremath{\alpha}}_{0}+{\ensuremath{\alpha}}_{\ensuremath{-}}=1$, provided that the interaction strength $\ensuremath{\mu}$ is smaller than a critical value. The saddle index ${n}_{s}$ is equal to ${\ensuremath{\alpha}}_{0}$ and its distribution function has a maximum at ${n}_{s}^{\mathrm{max}}=1∕3$. The density $p(e)$ of stationary points with energy per particle $e$, as well as…
Theoretical Study of the Electronic Spectrum of trans-Stilbene
1997
The electronic spectrum of trans-stilbene in the energy range up to 6 eV has been studied using multiconfigurational second-order perturbation theory (CASPT2). The study includes a geometry determination of the ground state. In all, 12 singlet and one triplet excited states were studied. The calculated spectrum makes it possible to assign the valence excited singlet states corresponding to the three bands observed in the low-energy region of the one-photon absorption spectrum. The most intense feature of the calculated spectrum corresponds to the 11Ag → 21Bu transition at 4.07 eV. The weakly allowed 11Bu state was found 0.3 eV below 21Bu. Transition to the 31Ag state, computed at 4.95 eV, i…
Molecule-like photodynamics of Au102(pMBA)44 nanocluster.
2015
Photophysical properties of a water-soluble cluster Au102(pMBA)44 (pMBA = para-mercaptobenzoic acid) are studied by ultrafast time-resolved mid-IR spectroscopy and density functional theory calculations in order to distinguish between molecular and metallic behavior. In the mid-IR transient absorption studies, visible or near-infrared light is used to electronically excite the sample, and the subsequent relaxation is monitored by studying the transient absorption of a vibrational mode in the ligands. Based on these studies, a complete picture of energy relaxation dynamics is obtained: (1) 0.5-1.5 ps electronic relaxation, (2) 6.8 ps vibrational cooling, (3) intersystem crossing from the low…
Role of Vibrational Dynamics in Electronic Relaxation of Cr(acac)3
2015
Ultrafast energy relaxation of Cr(acac)3 dissolved in tetrachloroethylene (TCE) is studied by time-resolved infrared (TRIR) spectroscopy by using electronic and vibrational excitation. After electronic excitation at 400 or 345 nm, the ground state recovers in two time scales: 15 ps (major pathway) and 800 ps (minor pathway), corresponding to fast electronic transition to the ground state and intermediate trapping on the long-lived (2)E state followed by intersystem crossing (ISC) to the ground state. The quantum yield for the fast recovery of the ground state depends on the excitation wavelength, being higher for 345 nm. Vibrational cooling (VC) occurs on the electronic excited states with …