Electronic spectroscopy and excited state dynamics of the Al–H2/D2 complex

Tan, Xiaofeng; Dagdigian, Paul J.; Alexander, Millard H.

doi:10.1039/b008488n

Cited by 13 publications

(16 citation statements)

References 43 publications

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“…18,22,[58][59][60][61][62][63] The para-H 2 molecule is spherically symmetric and cannot orient to sample the most attractive orientations (at least without mixing in the higher j = 2 rotational level). Alternatively, because of this spherical symmetry, the j = 0 state of H 2 lacks a quadrupole moment.…”

Section: B Resultsmentioning

confidence: 99%

The interaction of OH(X2Π) with H2: Ab initio potential energy surfaces and bound states

Kłos

Alexander

Avoird

et al. 2014

The Journal of Chemical Physics

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For the interaction of OH(X 2 ) with H 2 , under the assumption of fixed OH and H 2 bond distances, we have determined two new sets of four-dimensional ab initio potential energy surfaces (PES's). The first set of PES's was computed with the multi-reference configuration interaction method [MRCISD+Q(Davidson)], and the second set with an explicitly correlated coupled cluster method [RCCSD(T)-F12a] sampling the subset of geometries possessing a plane of symmetry. Both sets of PES's are fit to an analytical form suitable for bound state and scattering calculations. The CCSD(T) dissociation energies (D 0 ) of the OH-para-H 2 and the OH-ortho-H 2 complexes are computed to be 36.1 and 53.7 cm −1 . The latter value is in excellent agreement with the experimental value of 54 cm −1 .

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Section: B Resultsmentioning

confidence: 99%

The interaction of OH(X2Π) with H2: Ab initio potential energy surfaces and bound states

Kłos

Alexander

Avoird

et al. 2014

The Journal of Chemical Physics

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“…The apparatus in which these experiments were carried out has been described in detail previously. − In brief, the gallium dimer was prepared in a pulsed, free-jet supersonic expansion (0.2 mm diameter orifice) of mixtures of trimethylgallium (TMG, Strem), hydrogen, and helium. Deuterium and argon in various seed gas mixtures were also employed in place of hydrogen.…”

Section: Methodsmentioning

confidence: 99%

“…In the course of a search for the electronic spectrum of the Ga−H 2 van der Waals complex, following our studies of the Al−H 2 complex by predissociation spectioscopy, − we have observed electronic transitions of the gallium dimer in the 33 600−36 800 cm -1 wavenumber range. As mentioned above, the published spectroscopic information available on Ga 2 is quite limited.…”

Section: Introductionmentioning

confidence: 97%

Electronic Spectrum of the Gallium Dimer

Tan

Dagdigian

2003

J. Phys. Chem. A

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A study of the electronic spectrum of the gallium dimer in the 33 600-36 800 cm -1 spectral range is presented. The dimer was prepared in a pulsed, free-jet supersonic beam and detected by laser fluorescence excitation and depletion spectroscopy. All observed excited vibronic levels predissociate, and the transitions were detected by observation of Ga 5s f 4p atomic emission. Four excited-state progressions were observed, and it was possible to assign the excited-state vibrational quantum numbers on the basis of observed isotope shifts for two of the four progressions. Through comparison of the results with available quantum chemical calculations, these two progressions were assigned as electronic transitions to the 3 3 Π g and 2 1 Π g states from the ground X 3 Π u state. A Franck-Condon analysis was performed to determine the equilibrium internuclear separation of the 3 3 Π g state. An upper limit for the Ga 2 dissociation energy, D e ′′ < 8891 cm -1 , was derived. This bound is consistent with previous experimental and computational estimates of the dissociation energy.

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“…Nevertheless, as the H 2 bond is elongated to 0.9 Å , the energy barrier is reduced substantially and further configurational mixing between the orbital components of the 4p and 3d state with the same symmetry facilitates non-adiabatic Alkaline-earth atom-molecule reactions 305 transition between 5 1 A 0 (or 2 1 B 2 ) and 2 1 A 0 (or 1 1 B 2 ) surfaces in the repulsive limbs [58,59]. Thus, reactive collisions may take place only when H 2 (v ¼ 0) stretches to its outer turning point.…”

Section: -C Lin and A Gonza´lez Uren˜amentioning

confidence: 99%

Dynamical and stereodynamical studies of alkaline-earth atom–molecule reactions

Lin

Ureña

2007

International Reviews in Physical Chemistry

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Alkaline-earth atom molecule reactions have been extensively investigated since the early days of reaction dynamics. Though these reactions have many similarities to those of corresponding alkali atoms, as one would expect from their low ionization potential, there are important differences due to the presence of the two valence electrons in the alkaline-earth atom. This feature confers a distinct dynamical or stereodynamical behaviour whose basic description and analysis is the main objective of this article. The adopted approach is phenomenological based on the huge body of data revealed by modern crossed-beam and laser pump and probe techniques with no intention to be comprehensive but rather to put into context both authors' work. The paper starts with a resume´of the experimental approaches followed by a visit to full-collision studies under gas cell, beam-gas and crossed-beam arrangements. Detailed analysis and discussion is given of the M þ H 2 (M ¼ Ca, Mg) ! MH þ H reaction family whose dynamics is discussed using their Potential Energy Surfaces. In these studies care was taken to discuss the most relevant features of the molecular reaction dynamics with emphasis on the energy selectivity and on the stereodynamical (vectorial) nature of the reaction. To this end the available data are discussed in light of topological features of the underlying potential energy surface favouring either insertion or abstraction mechanisms. Particular attention is paid to the discussion of alkaline-earth atom reactions with halogen containing molecules. In these reactions the presence of two valence electrons leads to reaction channels, as chemiluminescent or chemi-ionization reactions, which are specifically associated with the transfer of the more energetic (inner harpooning) electron, whose dynamics or stereodynamics pattern differs from those of reaction channels associated to the transfer of the first, less energetic electron as, for example, in ion-pair reactions. A full section of the paper is dedicated to photo-induced intracluster reactions and, in particular, to the transition state dynamics of the prototype Ba . . . FCH 3 þ h ! BaF þ CH 3 reaction investigated in great detail by both nanosecond and femtosecond photo-ion and photo-electron pump and probe techniques. For this system the combination of these ultrahigh resolution techniques with isotopic labelling and ab initio calculations allowed the deciphering of its ultrafast reaction mechanism. Finally, the paper ends with some concluding remarks based on the observed propensity rules or general trends found in these alkaline-earth atom reactions.

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Electronic spectroscopy and excited state dynamics of the Al–H2/D2 complex

Cited by 13 publications

References 43 publications

The interaction of OH(X2Π) with H2: Ab initio potential energy surfaces and bound states

The interaction of OH(X2Π) with H2: Ab initio potential energy surfaces and bound states

Electronic Spectrum of the Gallium Dimer

Dynamical and stereodynamical studies of alkaline-earth atom–molecule reactions

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