"Dougle-Rydberg" molecular anions

Gutowski, Maciej; Simons, Jack; Hernández, R. Pomés; Taylor, Hugh L.

doi:10.1021/j100333a004

Cited by 34 publications

(18 citation statements)

References 3 publications

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“…Dissociation of NH; to produce H-+ NH3 is exothermic, but the barrier is larger than in the neutral NH, case for reasons described in ref 4. Dissociation of NH; to produce H-+ NH3 is exothermic, but the barrier is larger than in the neutral NH, case for reasons described in ref 4.…”

Section: Introductionmentioning

confidence: 97%

Rydberg bonding in ammonium dimer ((NH4)2)

Boldyrev¹,

Simons²

1992

J. Phys. Chem.

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Chemical binding of two monovalent Rydberg species to form a singlet-state Rydberg dimer molecule is predicted to be possible. Ab initio electronic structure methods that include electron correlation (at levels up through QCISD(T)/6-31++G**// MP2(fu11)/6-31++GS* + ZPE) are shown to be essential to achieving a proper description of such bonding. The (NH4)2 molecule, selected as the prototype for this study, is shown to be bound with respect to its Rydberg-species fragments, 2NH4, by 7.5-9.7 kcal/mol, depending on the level of treatment of electron correlation, and to be electronically stable (by ca. 4.3 eV) with respect to (NH4)2+ at the neutral's equilibrium geometry. The (NH4)2 Rydberg dimer is thermodynamically unstable with respect to 2NH3 + H2 by 86-89 kcal/mol mol yet possesses all real vibrational frequencies; it is thus a metastable molecule held together by a weak Rydberg bond. The dissociation energy of the (NH4)2+ cation to form NH4+ + NH4 is found to be larger than that of the neutral (NH4)2.

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Section: Introductionmentioning

confidence: 97%

Rydberg bonding in ammonium dimer ((NH4)2)

Boldyrev¹,

Simons²

1992

J. Phys. Chem.

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“…The cation and hypervalent neutral have very similar equilibrium geometries. This, of course, is expected based on our experience with such species [9] in which the attached electron occupies a nonbonding Rydberg-like orbital; 2. The hypervalent neutral lies ca.…”

Section: Relevant Potential Energy Curvesmentioning

confidence: 88%

Low‐energy (0.1 eV) electron attachment SS bond cleavage assisted by Coulomb stabilization

Sawicka

Berdys-Kochanska

Skurski

et al. 2005

Int J of Quantum Chemistry

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Electron capture by the ion H 3 C-S-S-CH 2 -CH 2 -NH 3ϩ at either the ϪNH 3 ϩ site (to form the Rydberg radical H 3 C-S-S-CH 2 -CH 2 -NH 3 ) or into the S-S antibonding * orbital is shown to be able to produce the same S-S bond fragmentation products H 3 C-S and HS-CH 2 -CH 2 -NH 2 , albeit by very different pathways. Capture into the S-S * orbital is, in the absence of the nearby positive site, endothermic by approximately 0.9 eV and leads to an electronically metastable anion that can undergo dissociation or autodetachment. In contrast, in the presence of the stabilizing Coulomb potential provided by the nearby NH 3 ϩ site, electron attachment into the S-S * orbital is rendered exothermic. As a result, as we have shown in this paper, the effective cross sections for forming the H 3 C-S and HS-CH 2 -CH 2 -NH 2 products via attachment at the ϪNH 3 ϩ and S-S * sites are predicted to be comparable for our model compound. Moreover, we predict that the * site will become more amenable to electron attachment compared with the ϪNH 3 ϩ site for compounds in which the distance between the S-S bond and the protonated amine is larger than in our cation. These findings and insights should be of substantial value to workers studying bond cleavage rates and fragmentation patterns in gaseous positively charged samples of peptides and proteins.

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“…Some time ago, 10 we discovered NH 4 − through its anion photoelectron spectrum, and we interpreted it as described above. Theoretical studies by Ortiz, 11 Gutowski et al, 12 and Matsunaga and Gordon 13 all supported that in-terpretation. In the meantime, we discovered four more double Rydberg anion analogs, having the stoichiometry, ͑N n H 3n+1 ͒ − , n =2-5.…”

Section: Two New Double Rydberg Anions Plus Access To Excited States mentioning

confidence: 90%

Two new double Rydberg anions plus access to excited states of neutral Rydberg radicals via anion photoelectron spectroscopy

Radisic

Stokes

Bowen

2005

The Journal of Chemical Physics

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We have observed and characterized two new double Rydberg anions N6H19- and N7H22- through their anion photoelectron spectra. The vertical detachment energies of these anions were found to be 0.443 and 0.438 eV, respectively. In addition, for three of the seven double Rydberg anions now known, we measured photodetachment transitions not only to the ground electronic states of their corresponding neutral Rydberg radicals but also to their first electronically excited states. In each spectrum, the energy spacing between the resulting peaks provided the ground-to-first electronically excited-state transition energy for the double Rydberg anion's corresponding neutral Rydberg radical. For the radicals, N4H13, N5H16, and N6H19, the spacings were found to be 0.83, 0.70, and 0.67 eV, respectively. These values are in excellent agreement with ground-to-first excited-state transition energies measured in absorption for the same neutral Rydberg radicals by Fuke and co-workers [Eur. Phys. J. D 9, 309 (1999); J. Phys. Chem. A 106, 5242 (2002).] The duplication of this neutral Rydberg property by photodetachment of double Rydberg anions further confirms that double Rydberg anions are indeed the negative ions of their corresponding neutral Rydberg molecules and cluster-like systems.

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"Dougle-Rydberg" molecular anions

Cited by 34 publications

References 3 publications

Rydberg bonding in ammonium dimer ((NH4)2)

Rydberg bonding in ammonium dimer ((NH4)2)

Low‐energy (0.1 eV) electron attachment SS bond cleavage assisted by Coulomb stabilization

Two new double Rydberg anions plus access to excited states of neutral Rydberg radicals via anion photoelectron spectroscopy

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