Search results for "Triplet state"
showing 10 items of 118 documents
Vibrational relaxation of Na2 molecules in a triplet state: collisional transfer from a mixed A 1Σu+ − b3Πu gateway level to long-lived levels of b 3…
1997
Abstract Collision-induced vibrational transitions of Na2 within the b 3Π1u state have been observed in a free jet expansion, using two CW dye lasers for the pump and probe steps. The b-state is entered by the pump laser using a low mixed ( A 1 Σ u + − b 3 Π u ) level as a gateway. The occupations of various v′,J′-levels are studied as functions of the position in the flowing gas. The radiative lifetimes of Na2 in levels which had been populated by vibrational relaxation are found to be very long (> 4 μs). Cross-sections are estimated for vibrationally inelastic collisions with Na and Ar atoms.
Photoinduced interfacial electron injection in RuN3–TiO2 thin films: Resolving picosecond timescale injection from the triplet state of the protonate…
2008
Using femtosecond transient absorption spectroscopy we have studied light-induced electron injection from the sensitizer RuN3 and its partly deprotonated tetrabutylamonium salt to nano-structured TiO2 film. Previous studies have suggested significant differences in electron injection dynamics for these dyes and some results have indicated that aggregation of the sensitizer may lead to slow injection. By measuring transient absorption spectra and kinetics of RuN3 and RuN3-TBA in solution and attached to TiO2 film we show that the electron injection dynamics are very similar for the two forms of the dye and that aggregation has only moderate effects on the electron transfer dynamics. (c) 2008…
Electron Transfer from the Singlet and Triplet Excited States of Ru(dcbpy)2(NCS)2into Nanocrystalline TiO2Thin Films
2002
Time-resolved absorption spectroscopy was used to study the femtosecond and picosecond time scale electron injection from the excited singlet and triplet states of Ru(dcbpY)(2)(NCS)(2) (RuN3) into titanium dioxide (TiO2) nanocrystalline particle film in acetonitrile. The fastest resolved time constant of similar to30 fs was shown to reflect a sum of two parallel ultrafast processes, nonergodic electron transfer (ET) from the initially excited singlet state of RuN3 to the conduction band of TiO2 and intersystem crossing (ISC). The branching ratio of 1.5 between the two competing processes gives rate constants of 1/50 fs(-1) for ET and 1/75 fs(-1) for ISC. Following the ultrafast processes, a…
Ab initio calculations of zero-field splitting parameters in linear polyacenes
2003
Abstract The results of ab initio calculations of zero-field splitting (ZFS) parameters are presented for the linear polyacenes from benzene to pentacene. We show how the electron spin–spin (SS) parameters can be efficiently obtained from restricted high-spin open-shell wave functions (ROHF), and present calculations of these, comparing with the results of a recent multi-configurational self-consistent field approach. The SS parameters are obtained from electron SS coupling strengths evaluated as expectation values over the wave functions and from state-to-state spin–orbit (SO) interactions. The results for the two lowest triplet states of naphthalene demonstrate that excellent values can b…
Spin State and Ligand Dissociation in [CpCoL2] Complexes (L = PH3, H2C=CH2): A Computational Study
1999
International audience; The relative energies of [CpCoL] compounds (L = PH3, H2C=CH2) were calculated at the DFT/B3LYP level of theory. The triplet spin state was found to be favored over the singlet by between 33.0 and 21.0 kcal mol−1 for both fixed and optimized geometries. The basis set size was found to be important for the energy calculations, particularly when the energetics of ligand dissociation was examined. The role of the triplet spin state in facilitating the ligand dissociation process is discussed.
Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene
1993
A newly proposed quantum chemical approach for ab initio calculations of electronic spectra of molecular systems is applied to the molecules ethene, trans‐1,3‐butadiene, and trans‐trans‐1,3,5‐hexatriene. The method has the aim of being accurate to better than 0.5 eV for excitation energies and is expected to provide structural and physical data for the excited states with good reliability. The approach is based on the complete active space (CAS) SCF method, which gives a proper description of the major features in the electronic structure of the excited state, independent of its complexity, accounts for all near degeneracy effects, and includes full orbital relaxation. Remaining dynamic ele…
Growth of paramagnetic defects by gamma rays irradiation in oxygen-deficient silica
2005
Abstract We report an electron paramagnetic resonance (EPR) study of gamma rays irradiation effects on an oxygen-deficient silica obtained from fused quartz. We have found that three types of E′ centers, E α ′ , E γ ′ and E δ ′ , and a paramagnetic defect in a spin triplet state (S = 1) are induced. The EPR signals dependence on the microwave power have been investigated. The concentrations of these centers as a function of gamma ray irradiation show that for high dose a limit value is reached suggesting a generation process from precursors.
Ab initio SCF and CI calculations on the barrier to internal rotation of 1,3-butadiene
1972
Ab initio SCF and CI calculations employing a set of gaussian lobe functions have been carried out for the ground and excited states of five geometrical C4H6-structures occurring in the course of rotation from cis-butadiene to the trans-isomer. The rotational potential curves are discussed for the ground and excited states. Particularly the potential curve of the lowest triplet state is considered in this connection thereby substantiating quantitatively the proposed mechanism for induced dimerisation of C4H6. Possible assignments of the lowest singlet excited states in trans-butadiene are discussed.
Oxidation of small gas phase Pd clusters: A density functional study
2006
The adsorption sites of O2 on neutral PdN clusters (N = 1–4) were studied using spin density functional theory. Only for Pd1O2 molecular adsorption is found to be favorable. For Pd2–4O2 dissociative adsorption with the oxygen sitting on Pd bridge sites is preferred. Most Pd clusters remain in the same high spin states found for pure gas phase Pd clusters. Only the ground state of Pd4O2 increase its spin from a triplet to a quintet state. For molecular adsorption the O–O bond gets activated to a superoxo-like state.
Electronic aspects of the hydride transfer mechanism. III. Ab-initio analytical gradient studies of the cyclopropenyl-cation/LiH with 4-31G and 3-21+…
1988
Abstract Hydride transfer reaction have been studied in sections of the energy hypersurface of cyclopropenyl cation and lithium hydride at 4-31G and 3-21+G basis set levels. The diffuse component has enforced the idea of an hydride-ion as being the particle transferred in the ground electronic state. Calculations on the first triplet state suggest a transfer mechanism mediated by one-electron followed by an hydrogen atom transfer. The change of basis set does not affect structural and energetics aspects of the reacting system except for the transferred particle, where, for some molecular complexes, the electronic distribution can be described as a hydride ion cementing two electron defficie…