Triplet Potential Curves Research Articles

Contrasting the wide Feshbach resonances inLi6andLi7

We compare and contrast the wide Fehbach resonances and the corresponding weakly bound states in the lowest scattering channels of ultracold $^6$Li and $^7$Li. We use high-precision measurements of binding energies and scattering properties to determine new interaction potentials, incorporating non-Born-Oppenheimer terms to account for the failure of mass scaling between $^6$Li and $^7$Li. Correction terms are needed for both the singlet and the triplet potential curves. The universal formula relating binding energy to scattering length is not accurate for either system. The $^6$Li resonance is open-channel-dominated and the van der Waals formula of Gao [J. Phys. B 37, 4273 (2004)] gives accurate results for the binding energies across much of the resonance width. The $^7$Li resonance, by contrast, is weakly closed-channel-dominated and a coupled-channels treatment of the binding energies is required. Plotting the binding energies in universal van der Waals form helps illustrate subtle differences between the experimental results and different theoretical forms near the resonance pole.

Ultrafast Nonadiabatic Dynamics of [FeII(bpy)3]2+ in Solution

The ultrafast relaxation of aqueous iron(II)-tris(bipyridine) upon excitation into the singlet metal-to-ligand charge-transfer band (1MLCT) has been characterized by femtosecond fluorescence up-conversion and transient absorption (TA) studies. The fluorescence experiment shows a very short-lived broad 1MLCT emission band at approximately 600 nm, which decays in < or =20 fs, and a weak emission at approximately 660 nm, which we attribute to the 3MLCT, populated by intersystem crossing (ISC) from the 1MLCT state. The TA studies show a short-lived (<150 fs) excited-state absorption (ESA) below 400 nm, and a longer-lived one above 550 nm, along with the ground-state bleach (GSB). We identify the short-lived ESA as being due to the 3MLCT state. The long-lived ESA decay and the GSB recovery occur on the time scale of the lowest excited high-spin quintet state 5T2 lifetime. A singular value decomposition and a global analysis of the TA data, based on a sequential relaxation model, reveal three characteristic time scales: 120 fs, 960 fs, and 665 ps. The first is the decay of the 3MLCT, the second is identified as the population time of the 5T2 state, while the third is its decay time to the ground state. The anomalously high ISC rate is identical in [RuII(bpy)3]2+ and is therefore independent of the spin-orbit constant of the metal atom. To reconcile these rates with the regular quasi-harmonic vibrational progression of the 1MLCT absorption, we propose a simple model of avoided crossings between singlet and triplet potential curves, induced by the strong spin-orbit interaction. The subsequent relaxation steps down to the 5T2 state dissipate approximately 2000 cm-1/100 fs. This rate is discussed, and we conclude that it nevertheless can be described by the Fermi golden rule, despite its high value.

Exploring excited-state hydrogen atom transfer along an ammonia wire cluster: Competitive reaction paths and vibrational mode selectivity

The excited-state hydrogen-atom transfer (ESHAT) reaction of the 7-hydroxyquinoline(NH(3))(3) cluster involves a crossing from the initially excited (1)pipi(*) to a (1)pisigma(*) state. The nonadiabatic coupling between these states induces homolytic dissociation of the O-H bond and H-atom transfer to the closest NH(3) molecule, forming a biradical structure denoted HT1, followed by two more Grotthus-type translocation steps along the ammonia wire. We investigate this reaction at the configuration interaction singles level, using a basis set with diffuse orbitals. Intrinsic reaction coordinate calculations of the enol-->HT1 step predict that the H-atom transfer is preceded and followed by extensive twisting and bending of the ammonia wire, as well as large O-H...NH(3) hydrogen bond contraction and expansion. The calculations also predict an excited-state proton transfer path involving synchronous proton motions; however, it lies 20-25 kcal/mol above the ESHAT path. Higher singlet and triplet potential curves are calculated along the ESHAT reaction coordinate: Two singlet-triplet curve crossings occur within the HT1 product well and intersystem crossing to these T(n) states branches the reaction back to the enol reactant side, decreasing the ESHAT yield. In fact, a product yield of approximately 40% 7-ketoquinoline.(NH(3))(3) is experimentally observed. The vibrational mode selectivity of the enol-->HT1 reaction step [C. Manca, C. Tanner, S. Coussan, A. Bach, and S. Leutwyler, J. Chem. Phys. 121, 2578 (2004)] is shown to be due to the large sensitivity of the diffuse pisigma(*) state to vibrational displacements along the intermolecular coordinates.

Linewidths in the Electron Paramagnetic Resonance Spectrum of Gaseous Atomic Hydrogen

A theory of the paramagnetic linewidth in gaseous atomic hydrogen, based on the theory of Baranger, and on an expansion of the spin correlation function in powers of the density is presented. To the approximations considered, the line shape is Lorentzian, the linewidth is proportional to the H atom density, and the relevant cross section involves an interference between the scattered amplitudes from the singlet and triplet potential curves. Comparison with experiment yields a velocity averaged cross section of 28.3×10—16 cm2 at 325°K. This value is compared to other estimates found in the literature.