Theoretical study of the binding of an electron to a molecular dipole: LiCl−

Jordan, Kenneth D.; Luken, William L.

doi:10.1063/1.432599

Cited by 136 publications

(78 citation statements)

References 16 publications

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“…It has been shown that, within the Born-Oppenheimer (BO) approximation, a dipole moment greater than 1.625 D possesses an infinite number of bound anionic states, [47][48][49][50][51] although the more practical critical value required to experimentally observe a dipole-bound anion was found to be slightly larger, about 2.5 D. 43,52 Jordan and Luken demonstrated that the loosely bound electron in a dipole-bound state occupies a diffuse orbital localized mainly on the positive side of the dipole. 28 This finding was confirmed by many recent studies. The role of non-BO coupling has been studied by Garrett, who concluded that such couplings are negligible for dipole-bound states with electron binding energies (E bind 's) much larger than the molecular rotational constants.…”

Section: Hydrazine and Its Tautomersupporting

confidence: 80%

“…The diffuse character of the orbital describing the loosely bound electron (see Figure 2) necessitates the use of extra diffuse basis functions having very low exponents. 28 In addition, the basis set chosen to describe …”

Section: Decomposition Of E Bind Into Various Physical Componentsmentioning

confidence: 99%

“…Dipole-Bound Anions. The binding of electrons to polar molecules has been addressed in many theoretical [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] and experimental 43-47 studies. It has been shown that, within the Born-Oppenheimer (BO) approximation, a dipole moment greater than 1.625 D possesses an infinite number of bound anionic states, [47][48][49][50][51] although the more practical critical value required to experimentally observe a dipole-bound anion was found to be slightly larger, about 2.5 D. 43,52 Jordan and Luken demonstrated that the loosely bound electron in a dipole-bound state occupies a diffuse orbital localized mainly on the positive side of the dipole.…”

Section: Hydrazine and Its Tautomermentioning

confidence: 99%

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Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study

1999

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The possibility of electron binding to the HNNH 3 and H 2 NNH 2 tautomers of hydrazine was studied at the coupled cluster level of theory with single, double, and noniterative triple excitations. The HNNH 3 tautomer, with a dipole moment of 5.4 D, binds an electron by 1076 cm -1 whereas the H 2 NNH 2 tautomer forms neither a dipole-nor valence-bound anionic state. It is suggested that the HNNH 3 tautomer, which is kinetically stable but thermodynamically unstable relative to H 2 NNH 2 , may be formed by photodetachment from the N 2 H 4 -species examined in this work.

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Section: Hydrazine and Its Tautomersupporting

confidence: 80%

Section: Decomposition Of E Bind Into Various Physical Componentsmentioning

confidence: 99%

Section: Hydrazine and Its Tautomermentioning

confidence: 99%

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Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study

1999

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“…Jordan and Luken demonstrated that the loosely bound electron in a dipole-bound state occupies a diffuse orbital localized mainly on the positive side of the dipole [17]. This finding was confirmed by many subsequent studies.…”

Section: Dipole-bound Anionssupporting

confidence: 71%

Are HBO⁻and BOH⁻electronically stable?

et al. 2003

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The binding of an excess electron to HBO and BOH was studied at the coupled cluster level of theory with single, double and non-iterative triple excitations and with extended basis sets to accommodate the loosely bound excess electron. The bent BOH molecule, with a dipole moment of 2.803 D, binds an electron by 39 cm À1 , whereas the linear HBO tautomer possesses a similar dipole moment (2.796 D) yet binds the electron by less than 1 cm À1 . It is therefore likely that HBO À is not stable when rotational energies are included whereas BOH À is for low rotational quantum numbers.

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“…The peptide ion dipole was shown to create a 0.4-0.5 V slant in the electrostatic field at distances of 15-20Å from the center of the ion, which can deform the Rydberg orbitals and steer the incoming electron towards regions of higher positive charge density. This is analogous to electron binding to a neutral molecular dipole that was analyzed by Jordan and Luken [75]. However, there is a difference between the ion and neutral dipoles in that electron binding in the ions is primarily due to the strong Coulomb interaction whereas the dipolar field represents an anisotropic perturbation that affects the electron density distribution.…”

Section: Electronic States and Dipolar Field Effectsmentioning

confidence: 99%

Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides

Moss

Chung

Wyer

et al. 2011

J. Am. Soc. Mass Spectrom.

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Electron transfer and capture mass spectra of a series of doubly charged ions that were phosphorylated pentapeptides of a tryptic type (pS,A,A,A,R) showed conspicuous differences in dissociations of charge-reduced ions. Electron transfer from both gaseous cesium atoms at 100 keV kinetic energies and fluoranthene anion radicals in an ion trap resulted in the loss of a hydrogen atom, ammonia, and backbone cleavages forming complete series of sequence z ions. Elimination of phosphoric acid was negligible. In contrast, capture of lowenergy electrons by doubly charged ions in a Penning ion trap induced loss of a hydrogen atom followed by elimination of phosphoric acid as the dominant dissociation channel. Backbone dissociations of charge-reduced ions also occurred but were accompanied by extensive fragmentation of the primary products. z-Ions that were terminated with a deaminated phosphoserine radical competitively eliminated phosphoric acid and H 2 PO 4 radicals. A mechanism is proposed for this novel dissociation on the basis of a computational analysis of reaction pathways and transition states. Electronic structure theory calculations in combination with extensive molecular dynamics mapping of the potential energy surface provided structures for the precursor phosphopeptide dications. Electron attachment produces a multitude of low lying electronic states in charge-reduced ions that determine their reactivity in backbone dissociations and H-atom loss. The predominant loss of H atoms in ECD is explained by a distortion of the Rydberg orbital space by the strong dipolar field of the peptide dication framework. The dipolar field steers the incoming electron to preferentially attach to the positively charged arginine side chain to form guanidinium radicals and trigger their dissociations.

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Theoretical study of the binding of an electron to a molecular dipole: LiCl−

Cited by 136 publications

References 16 publications

Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study

Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study

Are HBO⁻and BOH⁻electronically stable?

Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides

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Theoretical study of the binding of an electron to a molecular dipole: LiCl−

Cited by 136 publications

References 16 publications

Dipole-Bound Anion of the HNNH3 Isomer of Hydrazine. An Ab Initio Study

Dipole-Bound Anion of the HNNH3 Isomer of Hydrazine. An Ab Initio Study

Are HBO−and BOH−electronically stable?

Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides

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Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study

Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study

Are HBO⁻and BOH⁻electronically stable?