Potential curves for the ground and excited states of the NaN2 system

Habitz, Peter

doi:10.1016/0301-0104(80)80043-7

Cited by 62 publications

(19 citation statements)

References 14 publications

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“…The assumption that features of the potential surfaces determine this process gave rise to several theoretical investigations [3][4][5][6][7][8][9][10][11][12][13]. The review article by Campell et al [2] gives a summary of the recent experimental and theoretical work on this subject.…”

Section: Introductionmentioning

confidence: 99%

CARS spectroscopy of the NaH2 collision complex: the nature of the Na(32 P)H2 exciplex — ab initio calculations and experimental results

Vivie‐Riedle

Hering

Kompa

1990

Z Phys D - Atoms, Molecules and Clusters

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Atoms, Molecules zo,,°c.r,, and ClustersAbstract. CARS (Coherent Anti-Stokes Raman Scattering) has been used to analyze the rovibronic state distribution of H2 after collision with Na(3 2p). New lines, which do not correspond to H2 lines are observed in the CARS spectrum. The experiments point to the formation of a complex of Na(3 ZP)H z in A ZB 2 symmetry. Ab initio calculations of the A ZBz potential were performed. On this surface the vibrational spectra of the exciplex are evaluated. The observed lines can be attributed to vibrational transitions in the complex, in which combinational modes are involved. The connection of experimental and theoretical results indicates that a collisionally stabilized exciplex molecule is formed during the quenching process.

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Section: Introductionmentioning

confidence: 99%

CARS spectroscopy of the NaH2 collision complex: the nature of the Na(32 P)H2 exciplex — ab initio calculations and experimental results

Vivie‐Riedle

Hering

Kompa

1990

Z Phys D - Atoms, Molecules and Clusters

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“…In C s symmetry, the crossing is avoided and thus the system exhibits a conical intersection. A very nice ab initio analysis of wavefunctions in the vicinity of the conical intersection in the simple case of Na* þ N 2 quenching shows significant charge transfer from the metal atom to the nitrogen molecule, in geometries in which the N-N bond is stretched from its equilibrium distance [123]. The transfer of electronic energy proceeds via internal conversion to highly vibrationally-excited levels of the ground electronic state of the system.…”

Section: Dissociation Dynamics-electronic To Vibrational Energy Transfermentioning

confidence: 98%

Size-dependent reactivity in open shell metal-ion polar solvent clusters: spectroscopic probes of electronic-vibration coupling, oxidation and ionization

Farrar

2003

International Reviews in Physical Chemistry

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This review considers the spectroscopy and structure of clusters formed by stepwise addition of polar solvent molecules such as NH 3 , H 2 O, and CH 3 OH to effective one-electron chromophores that include the singly-charged alkaline earth cations Mg þ , Ca þ , and Sr þ ; atomic sodium; and the Rydberg molecule NH 4 . The absorption of photons by such species results in initial electronic excitation, followed by energy transfer to vibrational degrees of freedom, ultimately leading to dissociation. Experimental data are presented to support this electronic-tovibrational energy transfer mechanism. Wavelength-dependent photodissociation signals for all of these species exhibit a similar size-dependence in which large spectral red shifts are observed as the first solvation shell fills. An examination of ab initio calculations on a number of related systems, as well as theoretical models for charge transfer, suggests that non-covalent interactions of solvent molecules with the single valence electron of the cluster core lead to spontaneous ionization of the core with increasing cluster size. The process is analogous to the formation of solvated electrons in condensed phases. The collective results suggest that within the broad topic of solvation and the formation of solutions, clusters can provide a linkage between the properties of the gas phase and those of condensed phases.

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“…But the molecular nature of N2 is manifest in its electronic properties as well, in that the N2~ compound state is much lower in energy than, for example, Ar~ [19]. This results in "prestretching" of the N2 bond in the presence of the metal atom, as has been demonstrated for the Na-N2 system [4,5]. Although this will have implications for the details of the potentialenergy surfaces, their overall shape, and the collision mechanism sketched above, remains unaffected.…”

mentioning

confidence: 89%

“…Despite this, experimental progress in understanding the dynamics of these collisions has been slow, owing to the fact that the number of possible final states may be quite large and interference from groundstate processes can be overwhelming. Quenching of Na(3 2 / > ) has been studied in some detail in crossed-beam experiments involving a variety of molecular collision partners, and considerable insight has been obtained into the broad features of these processes [1][2][3][4][5]. Yet the difficulty in obtaining differential cross sections and the problems posed by near-resonant processes for conventional detection methods have hampered the full exploitation of the power of crossed-beam techniques in the study of these collisions.…”

mentioning

confidence: 99%

Dynamics of electronically inelastic collisions from 3D Doppler measurements

Suits¹,

P²,

Sublemontier³

et al. 1991

Phys. Rev. Lett.

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Flux-velocity contour maps were obtained for the inelastic collision process Ba( I / > i) + 02,N2 -* Ba( 3 / > 2) + 02,N2 from Doppler scans of scattered Ba( 3 F2) taken over a range of probe-laser directions in a crossed-beam experiment. The distributions suggest the importance of large-impact-parameter collisions and near-resonant energy transfer in the case of O2, while for N2 close collisions dominate despite the presence of an analogous near-resonant channel. The results represent the first direct experimental demonstration of a near-resonant quenching process.PACS numbers: 34.50. Lf, 34.50.Rk Quenching collisions between molecules and electronically excited atoms are nonadiabatic processes of central importance in laser physics and atmospheric and combustion chemistry. Despite this, experimental progress in understanding the dynamics of these collisions has been slow, owing to the fact that the number of possible final states may be quite large and interference from groundstate processes can be overwhelming. Quenching of Na(3 2 / > ) has been studied in some detail in crossed-beam experiments involving a variety of molecular collision partners, and considerable insight has been obtained into the broad features of these processes [1][2][3][4][5]. Yet the difficulty in obtaining differential cross sections and the problems posed by near-resonant processes for conventional detection methods have hampered the full exploitation of the power of crossed-beam techniques in the study of these collisions. Photodissociation studies have recently provided detailed insight into nonadiabatic interactions in "reverse" quenching processes [6]. Following pioneering experiments of Kinsey [7], Doppler spectroscopy has proved to be a versatile tool in the study of atom-atom collisions [8], photodissociation [9,10], and even reactive scattering [11,12], and offers a means of circumventing background problems inherent in the study of inelastic collisions. But the application of Doppler techniques has generally been limited to situations in which only one final state is involved and the final translational energies are known by virtue of the state probed. In that case, since the scattered species is confined to the surface of a sphere, the Doppler scan along the relative velocity vector can reveal the differential cross sections directly [7]. For the case in which numerous final states are involved and a range of product translational energies exist, no such simple relation holds: A range of center-of-mass velocities and angles may simultaneously satisfy the Doppler resonance condition [12,13]. We have successfully carried out investigation of such a case by taking Doppler scans over a range of probe-laser angles and applying the "forward-convolution" technique widely used in crossedbeam studies of reactive scattering [14,15] to derive angular and translational-energy distributions for systems in which the final translational energies are not known. We applied these methods to obtain complete contour maps of Ba( 3 P 2 ) flux f...

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Potential curves for the ground and excited states of the NaN2 system

Cited by 62 publications

References 14 publications

CARS spectroscopy of the NaH2 collision complex: the nature of the Na(32 P)H2 exciplex — ab initio calculations and experimental results

CARS spectroscopy of the NaH2 collision complex: the nature of the Na(32 P)H2 exciplex — ab initio calculations and experimental results

Size-dependent reactivity in open shell metal-ion polar solvent clusters: spectroscopic probes of electronic-vibration coupling, oxidation and ionization

Dynamics of electronically inelastic collisions from 3D Doppler measurements

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