Spectroscopic characterization of the potential energy functions of Ne2 Rydberg states in the vicinity of the Ne(1S0)+Ne(4p′) dissociation limits

The Journal of Chemical Physics

2012

Rotationally resolved pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the X 1/2, A(1) 3/2, and A(2) 1/2 electronic states of the ArXe(+) molecular ion have been recorded following resonant (1+1') two-photon excitation via selected rovibrational levels of the C 1 and D 0(+) states of selected isotopomers of the ArXe molecule. Using rovibronic selection and propensity rules for the photoionization out of these intermediate molecular states enabled the determination of the parity of the molecular-ion levels and of the magnitude and sign of the Ω-doubling constants of the coupled X 1/2 (p ≈ 4B) and A(2) 1/2 (p ≈ -2B) states of ArXe(+). The results indicate that these molecular-ion states can be approximately described using Mulliken's second variant of Hund's angular momentum coupling case (c), for which J(a), the total electronic and spin angular momentum of the two atoms, is a good quantum number (semi-united atom). The analysis of the rotational structure enabled the derivation of improved values of the dissociation energies, equilibrium distances, and molecular constants for the X 1/2, A(1) 3/2, and A(2) 1/2 states of ArXe(+).

Section: Introductionmentioning

confidence: 99%

Rotationally resolved PFI-ZEKE photoelectron spectroscopic study of the low-lying electronic states of ArXe+

Piticco

The Journal of Chemical Physics

2012

“…The diabatic potential-energy functions V d 6s (R) and V d 6p (R) were described by functions of the general form 14…”

Section: Perturbation Of the Vibrational Structure And Potential Modementioning

confidence: 99%

“…These functions possess a hump originating from the Pauli repulsion. 8,12,14 The cou-pling term a s,p (R) must vanish at R = ∞ and was represented by the function, (12) which is approximately constant at low R values and decreases to zero in the range between R s − W s and R s + W s , where R s and W s represent the center and the width of the switch function, respectively. In the calculations, R s and W s were kept fixed at the values R s = 5.25 Å and W s = 0.7 Å, respectively, so that the switch of the coupling constant from a 0 s,p to 0 occurs outside the range of internuclear distances described by the experimental data.…”

Section: Perturbation Of the Vibrational Structure And Potential Modementioning

confidence: 99%

“…Configurational mixing and spectral perturbations are extensive in the electronically excited states, and many states are predissociative and/or have potential-energy functions with multiple minima. 8,10,[12][13][14][15] Despite considerable progress in studies of the electronic structure and dynamics of rare-gas dimers since the first measurements of their vacuum ultraviolet electronic spectra, [16][17][18][19][20][21][22][23] the understanding of most band systems remains incomplete. Available predictions of the properties of electronically excited states by ab initio quantum chemistry [24][25][26][27] are not accurate enough to enable unambiguous spectral assignments.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Structure and dynamics of the electronically excited C 1 and D 0+ states of ArXe from high-resolution vacuum ultraviolet spectra

Piticco

Schäfer

The Journal of Chemical Physics

2012

Vacuum ultraviolet spectra of the C 1 ← X 0(+) and D 0(+) ← X 0(+) band systems of ArXe have been recorded at high resolution. Analysis of the rotational structure of the spectra of several isotopomers, and in the case of Ar(129)Xe and Ar(131)Xe also of the hyperfine structure, has led to the derivation of a complete set of spectroscopic parameters for the C 1 and D 0(+) states. The rovibrational energy level structure of the C 1 state reveals strong homogeneous perturbations with neighboring Ω = 1 electronic states. The analysis of isotopic shifts led to a reassignment of the vibrational structure of the C 1 state. The observation of electronically excited Xe fragments following excitation to the C state rotational levels of f parity indicates that the C state is predissociated by the electronic state of 0(-) symmetry associated with the Ar((1)S(0)) + Xe(6s(')[1/2](0) (o)) dissociation limit. The observed predissociation dynamics differ both qualitatively and quantitatively from the behavior reported in previous investigations. An adiabatic two-state coupling model has been derived which accounts for the irregularities observed in the rovibronic and hyperfine level structure of the C 1 state. The model predicts the existence of a second state of Ω = 1 symmetry, supporting several tunneling/predissociation resonances located ~200 cm(-1) above the C 1 state.

“…(1)]. In the case of the rare‐gas atoms He and Ne in their ground state, the scattering length is positive, and potential maxima arise at the maxima of the Rydberg electron probability density 7. The scattering length for the heavier rare gas atoms becomes progressively more negative with increasing size.…”

mentioning

confidence: 99%

A New Perspective on the Binding Power of an Electron

Hogan

2009

ChemPhysChem

Self Cite

1‐Hydroxy‐1,2‐benziodoxol‐3(1H)‐one (IBA) is an efficient terminal oxidant for gold‐catalysed, three‐component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem‐disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor‐based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced. In addition, the IBA‐derived co‐products can be recovered and recycled.