Radiative transition probabilities, lifetimes, and dipole moments for all vibrational levels in the X 1Σ+ state of the beryllium hydride ion

Potential energy, dipole moment, and electronic transition moment functions for the A 3Πand X3Σ- states of PH have been calculated from highly correlated electronic wavefunctions. The electric dipole moments in the vibrational ground state of PH are calculated to be 0.637 Debye (A 3Π) and 0.403 Debye (X3Σ-). The predicted rates of spontaneous emission between low lying vibrational states of the X state lie in the range of 46 to 109 sec-1 (PH) and 12 to 30 sec-1 (PD). The calculated radiative lifetime of the v' = 0 level in the A 3Π state of 400 ns is lower by about 10 percent than the most recent experimental value. The classical intersection of the 5Σ- and the A 3Πstate has been calculated to lie between v' = 2 and 3 with an expected uncertainty of about 500 cm−1, whereas the onset of the rotationally dependent predissociation lies at v' = 0, J' = 11.

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Energies and Electric Dipole Moments of the Bound Vibrational States of HN2+ and DN2+

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20080873 ◽

2008 ◽

Vol 73 (6-7) ◽

pp. 873-897 ◽

Cited By ~ 8

Author(s):

Vladimír Špirko ◽

Ota Bludský ◽

Wolfgang P. Kraemer

Keyword(s):

Dipole Moment ◽

Nearest Neighbor ◽

Energy Surface ◽

Dipole Moments ◽

Three Dimensional ◽

Vibrational States ◽

Spacing Distribution ◽

Triatomic Molecules ◽

Vibrational Levels ◽

Different Levels

The adiabatic three-dimensional potential energy surface and the corresponding dipole moment surface describing the ground electronic state of HN2+ (Χ1Σ+) are calculated at different levels of ab initio theory. The calculations cover the entire bound part of the potential up to its lowest dissociation channel including the isomerization barrier. Energies of all bound vibrational and low-lying ro-vibrational levels are determined in a fully variational procedure using the Suttcliffe-Tennyson Hamiltonian for triatomic molecules. They are in close agreement with the available experimental numbers. From the dipole moment function effective dipoles and transition moments are obtained for all the calculated vibrational and ro-vibrational states. Statistical tools such as the density of states or the nearest-neighbor level spacing distribution (NNSD) are applied to describe and analyse general patterns and characteristics of the energy and dipole results calculated for the massively large number of states of the strongly bound HN2+ ion and its deuterated isotopomer.

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Radiative transition probabilities in the O-like sequence

Astronomy and Astrophysics ◽

10.1051/0004-6361:20042100 ◽

2005 ◽

Vol 434 (1) ◽

pp. 365-376 ◽

Cited By ~ 9

Author(s):

E. Landi

Keyword(s):

Transition Probabilities ◽

Radiative Transition

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Infra-red chemiluminescence II. Spectroscopic data

Proceedings of the Royal Society of London Series A - Mathematical and Physical Sciences ◽

10.1098/rspa.1960.0206 ◽

1960 ◽

Vol 258 (1295) ◽

pp. 564-575 ◽

Cited By ~ 7

Keyword(s):

Transition Probabilities ◽

Molecular Spectroscopy ◽

Radiative Transition ◽

Absorption Data ◽

A Value ◽

Interaction Factor ◽

Infra Red ◽

Rotational Distribution ◽

Vibration Rotation ◽

First Time

The technique described in part I has been used to obtain constants of interest in molecular spectroscopy. The vibration-rotation interaction factor, F for HCl has been evaluated from the infra-red emission spectrum. The critical parameter in F is θ = M 0 / M 1 r e , where M 0 and M 1 are the first two coefficients in the electric dipole moment expansion about the equilibrium internuclear distance r e . A value of θ = + 1.12 ± 0.18 has been obtained. It is shown that for molecules with θ = +1 the total band intensity in emission is independent of the rotational distribution in the vibrational state from which the emission occurs. This has been made use of in evaluating radiative transition probabilities. For the HCl v (3-1) transition a value for | R 3 1 | 2 (= 1.60 x 10 -4 debye 2 ) was obtained for the first time. The same method yields a value of | R 2 1 | 2 / | R 2 0 | 2 = 204, in good agreement with an earlier estimate from absorption data.

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