Renner–Teller interaction, high angular momentum states and spin-orbit interaction in the electronic spectrum of ND₂

First principles determination of the NH2/ND2($\skew4\tilde A, \skew3\tilde X$Ã,X̃) branching ratios for photodissociation of NH3/ND3 via full-dimensional quantum dynamics based on a new quasi-diabatic representation of coupled ab initio potential energy surfaces

“…However, there is no question that the excited state ND 2 (Ã 2 A 1 ) is produced by photolysis of ND 3 around this energy (e.g., 193 nm), because its emission to its ground electronic state has been recorded. 23,25 The Rydberg tagging experiment is known to be less sensitive to slow D atoms, particularly when the detector was placed perpendicular to the beam direction. 17 With that in mind, the overall good agreement provides strong evidence for the accuracy of the PESs and their couplings.…”

“…Detailed measurements of the absorption spectra, 4-12 product internal state distributions, [13][14][15][16][17][18][19][20][21][22][23][24][25] and dissociation lifetimes 26,27 have been reported. Particularly relevant to the a) Authors to whom correspondence should be addressed.…”

Photodissociation of ND3 and ND2H at 193.3nm: Symmetry dependence of the rotational distributions and vibrational excitation of the ND2 () fragment

“…In our previous paper [21] we gave a detailed analysis of the fluorescence spectra of ND 2 obtained by the photolysis of ND 3 [20] by the Leone group. In the present paper we turned our attention to the analysis of the fluorescence spectra of ND 2 obtained by the photolysis of ND 2 H, to see whether there was clear evidence to the role of the fragmentation dynamics in the ND 2 emission from the unsymmetrical parent molecule.…”

“…The emission spectra recorded following the photolysis of ND 3 showed considerable repeating regularity in their structure [21], whereas those recorded following the photolysis of the unsymmetrical isotopologue, ND 2 H, exhibit far less regularity in their repetitive structure. One possible hypothesis is that as the trigonal symmetry of the parent molecule has been broken, efficient transfer of energy to motion about the b/c rotational axes of the ND 2 is much more likely, and may account for some of the complexity of the emission spectrum.…”

“…More recently a detailed analysis has been made of the fluorescence spectra of ND 2 obtained by the photolysis of ND 3 [21] using an excimer laser operating at 193.3 nm. In the present paper this analysis has been extended to the emission spectra of ND 2 obtained by the photolysis of ND 2 H. In the comparison of the emission spectra of ND 2 produced by the photolysis of ND 3 and ND 2 H Mordaunt et al [13,14] and Reid et al [17,18,20] have shown that the differing fragmentation energies of the NH bond in ND 2 H and the ND bond of ND 3 need to be taken into account.…”