Chemiluminescence and rotational alignment in Mn+O2: Direct observation of the MnO*(A′ 6Π) state

Spence, Matthew A.; Tomlinson, W. R.; Levy, Moshe

doi:10.1039/b102508m

Cited by 7 publications

(8 citation statements)

References 28 publications

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“…As presented previously, 21 the MnO 2 target yields an atomic beam which is much 'colder' than that from Mn, both in terms of velocity spread and internal state composition. In particular, the z 8 P J -a 6 S emission essentially disappears, the Mn* a 6 D J :a 4 D J ratio increases by a factor B2.3, 11,12 and the proportion of a 6 S atoms increases substantially, a feature which has allowed determination of the time-profile of the beam by laser-induced fluorescence on the a 6 S-z 6 P J transition at B403 nm. 21 s(E T 0 ) is then obtained by substituting N 0 (t), the flux I LIF (t)/t, for I b (t)/(G(t)t) in eqn (2).…”

Section: Procedures 1 Experimentalmentioning

confidence: 99%

“…1, and below which delay time the beam pulse is increasingly poorly defined. Analogously to Mn + Cl 2 , 10 O 2 11 and SO 2 , 12 we therefore limit our consideration of the 'cold' beam data to the range shown.…”

Section: Translational Excitation Function Measurementsmentioning

confidence: 99%

“…6 While a number of investigations have concerned reaction dynamics of ground state atoms, including the detection of electronic chemiluminescence, [1][2][3][7][8][9] relatively few have focused on the low-lying excited states of the reagents. Apart from work in this laboratory on Mn*(a 6 D J , z 8 P J , a 4 D J ) reactions, [10][11][12] the only recent experimental studies of that type to have come to our attention are those on Ti*(a 5 F J ) + NO, O 2 , N 2 O, 8,9 V*(a 4 F J ) + NO, 13 Cu*( 2 D 5/2,3/2 ) + ClF 14 and Zr*(z 3 F 2 0 ) + CH 3 F, 15 although there were some other investigations in earlier years. 1,7 For first row transition metal atoms at least, these excited states are the more interesting, as the ionisation energies are lower than for the ground states and the relatively unreactive .…”

Section: Introductionmentioning

confidence: 99%

“…In studies of Mn + halogens and halides, 10,[17][18][19][20][21][22] translational excitation functions s(E T ) for chemiluminescence in the MnF and MnCl A 7 P-X 7 S + , e 5 S + -a 5 S + , d 5 P-a 5 S + , c 5 S + -a 5 S + and b 5 P-a 5 S + band systems have been measured. Analysis of the data in terms of the multiple-line-of centres (MLC) expression [10][11][12][17][18][19][20][21]23 Y(E T ) = E T s(E T ) = P s k (E T À E k ),…”

Section: Introductionmentioning

confidence: 99%

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State-to-state chemiluminescence in reactions of Mn atoms with S2Cl2

Khanniche

Levy

2011

Phys. Chem. Chem. Phys.

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A combined experimental and time-dependent density functional theory (TDDFT) investigation of the title reaction is presented. Both 'hot' and 'cold' laser-ablated Mn atom beams have been employed to determine the translational excitation functions for production of MnCl*(c(5)Σ(+), d(5)Π, e(5)Δ, e(5)Σ(+), A(7)Π). Analysis in terms of the multiple line-of-centres approach shows that the 'hot' results are dominated by reactions of the second metastable state of Mn, z(8)P(J), all with very low thresholds; while the first metastable state, a(6)D(J), and the ground state, a(6)S, are the precursors in the 'cold' results, all with significant excess barriers. The post-threshold behaviour of most z(8)P(J) and a(6)D(J) reaction channels implies that the transition states shift forward with increasing collision energy. The TDDFT calculations suggest that, while Mn*(z(8)P(J), a(6)D(J)) insertion into the S-Cl bond is facile, the observed chemiluminescence channels mostly derive from abstraction in a preferred linear Mn-Cl-S configuration, and that the low z(8)P(J) thresholds originate from attractive but excited reagent potentials which either reach a seam of interactions in the product valley or (in the c(5)Σ(+) case) lead to an octet potential very close in energy to the product sextet. The excess barriers in the Mn*(a(6)D(J)) and Mn(a(6)S) reactions appear for the most part to derive from exit channel mixing with lower-lying product potentials. The observed transition state shifts are consistent with the system being forced to ride up the repulsive wall of the entrance valley as collision energy increases, the location of that wall being different for the z(8)P(J) and a(6)D(J) cases.

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Section: Procedures 1 Experimentalmentioning

confidence: 99%

Section: Translational Excitation Function Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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State-to-state chemiluminescence in reactions of Mn atoms with S2Cl2

Khanniche

Levy

2011

Phys. Chem. Chem. Phys.

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“…Ἡ μοναδικὴ μετέπειτα ἀξιόλογη θεωρητικὴ ἐργασία ἀνήκει στοῦς Bauschlicher καὶ Maitre 41. Οἱ λοιπὲς θεωρητικὲς μελέτες θεωροῦνται χαμηλῆς ποιότητος 39,47,166,167. Ὅλα τὰ δεδομένα τῆς ὑπάρχουσας βιβλιογραφίας συλλέγονται στὸν Πίνακα 7.1.…”

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Ηλεκτρονιακή δομή των οξειδίων ΜΟ 0, M=Sc, Ti, Cr, Mn, μέσω υπολογισμών πρώτων αρχών

Μηλιόρδος¹

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Applying the most reliable ab initio techniques, we studied the neutral, positively and negatively singly charged monoxides of four of the first row transition metals, ΜΟ0,± (Μ = Sc, Ti, Cr, Mn). In particular, we employed the multireference configuration interaction and single reference coupled cluster methodologies in conjunction with basis sets of quadruple?ζ quality. Correlating all valence electrons of both atoms, we constructed full potential energy curves of a total of 152 electronic states, providing spectroscopic constants, dissociation energies, bond distances, dipole moments (for the neutral species) and excitation energies for all of them. The inclusion of the 3s23p6 semi?core electrons in the CI procedure, as well as the influence of the scalar relativistic effects were taken into account selectively for some of them. The numerical results of the present study are compared favorably with the available experimental data, whereas they are more accurate and systematic than any other theoretical work in the previous literature. Concerning the electronic structure, the neutral and positive species of the examined oxides exhibit a clear ionic character, Μ+Ο? and Μ2+Ο? respectively, while for the anions the negative charge is located mainly on the oxygen atom, Μ?Ο?.

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An Overlooked Series of Gas Phase Diatomic Metal Oxide Ions that Are Long-lived

Schofield

2006

J. Phys. Chem. A

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Although the "Golden" years of spectroscopy and the major studies on ionization processes now are behind us, as with many branches of science, much yet remains to be gleaned from such topics that is both full of interest and of significance to present day research. Presented here is one such overlooked example, an observation that relates to both these fields. An analysis is presented for the periodic table concerning the gas-phase thermochemical nature of MO+ and MO2+ ions. Unexpectedly, a pattern of 18 elements has been identified that exhibit the potential for having long-lived MO+ ions. Normally such molecular ions are expected to decay extremely rapidly by dissociative recombination with electrons, but in particular, 12 of this group behave not like molecules but rather as atomic ions. These are the diatomic oxide ions of Sc, Y, La, Zr, Hf, Ce, Pr, Nd, Pm, Gd, Tb, and Th. In the gas phase, they decay by much slower three-body recombination channels. As may be noted, these elements are located in the first two columns of the transition elements, among the earlier rare earths and an actinide. From all the elements, UO2+ is the only dioxide ion that behaves similarly. These findings now elevate the potential importance of these ions and should facilitate their spectral characterization. Moreover, subsequent comparisons with spectra of well-known isoelectronic and isovalent neutral monoxides and other diatomics will help in the stimulation of further theoretical advances. In addition, once characterized, an ease of spectrally monitoring such ionic states will provide a useful analytical tool.

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Chemiluminescence and rotational alignment in Mn+O2: Direct observation of the MnO*(A′ 6Π) state

Cited by 7 publications

References 28 publications

State-to-state chemiluminescence in reactions of Mn atoms with S2Cl2

State-to-state chemiluminescence in reactions of Mn atoms with S2Cl2

Ηλεκτρονιακή δομή των οξειδίων ΜΟ 0, M=Sc, Ti, Cr, Mn, μέσω υπολογισμών πρώτων αρχών

An Overlooked Series of Gas Phase Diatomic Metal Oxide Ions that Are Long-lived

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