Observation of three weakly bound valence states of I2

Ridley, Trevor; Lawley, Kenneth P.; Donovan, Robert J.

doi:doi:10.1063/1.2795722

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Accounting for the dependence of P(E′,E) on the maximum impact parameter in classical trajectory calculations: Application to the H₂O–H₂O collisional relaxation

In this work we report a novel methodology that is able to predict how energy transfer transition probability density functions [P(E′,E)] change with the maximum impact parameter (bmax) used in trajectory calculations (TC’s). The method assumes that P(E′,E) can be described by a sum of exponential functions and that all the trajectories with an initial impact parameter beyond a certain critical value will contribute only to the elastic peak [P(E′,E) for E′ = E]. This approach is applied to H2O–...

Complete determination of the photoionization dynamics of a polyatomic molecule. I. Experimental photoelectron angular distributions from ¹A_u acetylene

Angle-resolved photoelectron spectra from rotationally selected 1Au state acetylene have been recorded using velocity-map imaging. Several Renner-Teller split vibrational bands have been observed and assigned, showing good agreement with previous zero kinetic energy photoelectron (ZEKE) work [ S. T. Pratt, P. M. Dehmer, and J. L. Dehmer, J. Chem. Phys. 99, 6233 (1993) ; S.-J. Tang, Y.-C. Chou, J. J.-M. Lin, and Y.-C. Hsu, ibid. 125, 133201 (2006) .] The extracted photoelectron angular distrib...

Structured emission in the gas phase to two weakly bound valence states that correlate with the third dissociation limit, I^*(²P_1/2)+I^*(²P_1/2), designated as (bb), from two third tier ion-pair states of I₂ correlating with I⁻(¹S₀)+I⁺(¹D₂), the 1_g(¹D₂), and F′0_u⁺(¹D₂) states, has been observed for the first time. The 1_u(bb) state is shown to be bound by 377±2 cm⁻¹ and molecular constants have been determined. Vibrational structure in the 0_g⁺(bb) state could not be resolved but the spectrum is consistent with the state being bound by 435 cm⁻¹. The relative integrated intensities of the emissions from both ion-pair states to various valence states have also been measured, and some aspects are rationalized in terms of the electronic configurations of the upper and lower states. Bound levels of a previously uncharacterized 1_g(ab) valence state have also been observed in emission from the γ1_u(³P₂) ion-pair state. The lower state is shown to be bound by 270±2 cm⁻¹ and molecular constants have been determined.

Article Outline

INTRODUCTION
EXPERIMENT
RESULTS AND DISCUSSION
1. Simulation of the fluorescence spectra
2. Emission from the 1_g(¹D₂) ion-pair state
3. Emission from the F′0_u⁺(¹D₂) ion-pair state
4. Emission from the γ1_u(³P₂) ion-pair state
5. Distribution of emission intensities
CONCLUSIONS

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KEYWORDS and PACS

Keywords

dissociation energies, iodine, valence bands, vibrational states

PACS

33.15.Mt

Rotation, vibration, and vibration-rotation constants
33.15.Fm

Bond strengths, dissociation energies
33.70.Fd

Absolute and relative line and band intensities

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http://dx.doi.org/10.1063/1.2795722

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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