Radiative lifetimes of the A 2Σ+12 and X22Π32 states of lead monohalides

Shestakov, O.; Demes, H.; Fink, E.H.

doi:10.1016/0301-0104(93)85092-m

Cited by 7 publications

(5 citation statements)

References 10 publications

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“…The calculations overestimate these quantities by 0.01-0.03 Å relative to experiment. 1 The agreement between corresponding computed vibrational frequencies is similar on a percentage basis for the two SO-CI treatments. A slight exception occurs for the A 2 ⌺ 1/2 ϩ state ͑16 cm Ϫ1 discrepancy͒, probably because the corresponding potential well characteristics are relatively sensitive to the description of large-r interactions, unlike the case for the X 2 ⌸ pair of ⍀ states.…”

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confidence: 59%

“…3͒ that this quantity should depend rather strongly on vЈ, and it would be highly desirable to check this result experimentally. The X 2 radiative lifetime has also been measured, 1,33 and a value of 0.36Ϯ0.05 ms has been found, some 72 times longer than for the A state's value. The present computed lifetime values are also given in Table VI as a function of vЈ.…”

Section: B Radiative Lifetimesmentioning

confidence: 99%

“…1 On the other hand, the opposite trend is observed for the X 2 2 ⌸ 3/2 state: 0.36Ϯ0.05 ms for PbF and 4.0Ϯ0.6 ms for PbI. 1 No explanation for these trends has yet been given, but it seems clear that it can best be sought by carrying out accurate calculations of the corresponding dipole transition moments for these systems. Over the past eight years, our research group has reported numerous calculations of radiative lifetimes for electronic and vibrational states of diatomic and triatomic molecules containing at least one heavy atom, beginning with a series of Group 15 halides, 2-5 hydrides [6][7][8] and oxides, [9][10][11] and more recently with various tellurium compounds, [12][13] BiNa 14 and TlH.…”

Section: Introductionmentioning

confidence: 99%

“…Fink and co-workers 1 have measured radiative lifetimes of the A and X 2 states of all four stable lead monohalides. The A 2 ⌺ ϩ -X 2 ⌸ is the key transition at the ⌳ -S level of treatment and its transition dipole moment value is shown as a function of r in Fig.…”

Section: A Transition and Dipole Momentsmentioning

confidence: 99%

“…It was found that the A state's lifetime decreases steadily with atomic number of the halogen atom, varying from 5.0Ϯ0.8 s for PbF to 0.13 Ϯ0.03 s for PbI. 1 On the other hand, the opposite trend is observed for the X 2 2 ⌸ 3/2 state: 0.36Ϯ0.05 ms for PbF and 4.0Ϯ0.6 ms for PbI. 1 No explanation for these trends has yet been given, but it seems clear that it can best be sought by carrying out accurate calculations of the corresponding dipole transition moments for these systems.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio spin-orbit CI calculations of the potential curves and radiative lifetimes of low-lying states of lead monofluoride

Das

Petsalakis

Liebermann

et al. 2002

The Journal of Chemical Physics

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The electronic structure of the lead monofluoride molecule is studied by means of ab initio configuration interaction ͑CI͒ calculations including the spin-orbit interaction. Potential-energy curves are generated for a large number of electronic states, of which only the X 1 2 ⌸ 1/2 ground and X 2 2 ⌸ 3/2 and A 2 ⌺ ϩ excited states have been observed experimentally. Two different methods are compared for the inclusion of spin-orbit effects in the theoretical treatment, a contracted CI which employs a basis of large-scale ⌳ -S eigenfunctions to form a rather small matrix representation of the full relativistic Hamiltonian ͑two-step approach͒, and a more computationally laborious technique which involves solution of a secular equation of order 250 000 S 2 eigenfunctions of different spin and spatial symmetry to achieve a potentially more evenly balanced description of both relativistic and electron correlation effects ͑one-step approach͒. In the present application, it is found that both methods achieve quite good agreement with measured spectroscopic constants for the X 1 , X 2 , and A states. The simpler of these methods is also employed to predict the radiative lifetimes of the latter two states. The key A 2 ⌺ ϩ -X 2 ⌸ transition moment in these calculations is found to vary strongly with internuclear distance and to vanish in the neighborhood of the respective equilibrium distances of both participating states. The computed lifetime for the A, vЈϭ0 state of 16 s overestimates the corresponding measured value by a factor of three, but those of higher vibrational states are found to decrease rather sharply with increasing vЈ, suggesting that only a slight displacement of the theoretical A -X transition moment curve is needed to explain the above discrepancy.

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mentioning

confidence: 59%

Section: B Radiative Lifetimesmentioning

confidence: 99%