An experimental study of hypervalent molecular clusters by neutralized ion beam spectroscopy: NH4(NH3)n and ND4(ND3)n for n = 1-3

Gregory I. Gellene; Richard F. Porter

doi:10.1021/j150670a035

An experimental study of hypervalent molecular clusters by neutralized ion beam spectroscopy: NH₄(NH₃)_n and ND₄(ND₃)_n for n = 1-3

Gregory I. Gellene, Richard F. Porter

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

67 Scopus citations

Abstract

Clusters of the form NH₄(NH₃)_n have been generated by neutralizing a fast beam of ions in the electron transfer reaction NH₄(NH₃)_n⁺ K_(g) → NH₄(NH₃)_n+ K⁺ (n = 1-3). Analysis of neutral beam scattering profiles and collisionally reionized mass spectra for NH₄(NH₃) and ND₄(ND₃) indicate that these clusters are formed in a distribution of metastable and dissociative states. The n = 1 cluster in its dissociative state has sufficient internal energy to break up to 2NH₃ + H without formation of the dimer (NH₃)₂. The species N₂D₆H decomposes by preferential loss of a H atom analogous to the dissociative behavior of ND₃H. The lifetimes of the metastable states of NH₄(NH₃) and ND₄(ND₃) are greater than 1 μs. From thermodynamic considerations the ionization potential of NH₄(NH₃) is estimated to be 4.0 ± 0.2 eV. As n increases, the ionization potentials for the clusters decrease to a value of about 2.5 eV for NH₄(NH₃)₃. Spectroscopic considerations suggest that NH₄(NH₃) and ND₄(ND₃) will exhibit an electronic absorption spectrum involving low-lying Rydberg states.

Original language	English
Pages (from-to)	6680-6684
Number of pages	5
Journal	Journal of physical chemistry
Volume	88
Issue number	26
DOIs	https://doi.org/10.1021/j150670a035
State	Published - 1984

Access to Document

10.1021/j150670a035

Cite this

@article{cccf5e901cd943d5ac0197088a5c9805,

title = "An experimental study of hypervalent molecular clusters by neutralized ion beam spectroscopy: NH4(NH3)n and ND4(ND3)n for n = 1-3",

abstract = "Clusters of the form NH4(NH3)n have been generated by neutralizing a fast beam of ions in the electron transfer reaction NH4(NH3)n+ K(g) → NH4(NH3)n+ K+ (n = 1-3). Analysis of neutral beam scattering profiles and collisionally reionized mass spectra for NH4(NH3) and ND4(ND3) indicate that these clusters are formed in a distribution of metastable and dissociative states. The n = 1 cluster in its dissociative state has sufficient internal energy to break up to 2NH3 + H without formation of the dimer (NH3)2. The species N2D6H decomposes by preferential loss of a H atom analogous to the dissociative behavior of ND3H. The lifetimes of the metastable states of NH4(NH3) and ND4(ND3) are greater than 1 μs. From thermodynamic considerations the ionization potential of NH4(NH3) is estimated to be 4.0 ± 0.2 eV. As n increases, the ionization potentials for the clusters decrease to a value of about 2.5 eV for NH4(NH3)3. Spectroscopic considerations suggest that NH4(NH3) and ND4(ND3) will exhibit an electronic absorption spectrum involving low-lying Rydberg states.",

author = "Gellene, {Gregory I.} and Porter, {Richard F.}",

year = "1984",

doi = "10.1021/j150670a035",

language = "English",

volume = "88",

pages = "6680--6684",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

number = "26",

}

TY - JOUR

T1 - An experimental study of hypervalent molecular clusters by neutralized ion beam spectroscopy

T2 - NH4(NH3)n and ND4(ND3)n for n = 1-3

AU - Gellene, Gregory I.

AU - Porter, Richard F.

PY - 1984

Y1 - 1984

N2 - Clusters of the form NH4(NH3)n have been generated by neutralizing a fast beam of ions in the electron transfer reaction NH4(NH3)n+ K(g) → NH4(NH3)n+ K+ (n = 1-3). Analysis of neutral beam scattering profiles and collisionally reionized mass spectra for NH4(NH3) and ND4(ND3) indicate that these clusters are formed in a distribution of metastable and dissociative states. The n = 1 cluster in its dissociative state has sufficient internal energy to break up to 2NH3 + H without formation of the dimer (NH3)2. The species N2D6H decomposes by preferential loss of a H atom analogous to the dissociative behavior of ND3H. The lifetimes of the metastable states of NH4(NH3) and ND4(ND3) are greater than 1 μs. From thermodynamic considerations the ionization potential of NH4(NH3) is estimated to be 4.0 ± 0.2 eV. As n increases, the ionization potentials for the clusters decrease to a value of about 2.5 eV for NH4(NH3)3. Spectroscopic considerations suggest that NH4(NH3) and ND4(ND3) will exhibit an electronic absorption spectrum involving low-lying Rydberg states.

AB - Clusters of the form NH4(NH3)n have been generated by neutralizing a fast beam of ions in the electron transfer reaction NH4(NH3)n+ K(g) → NH4(NH3)n+ K+ (n = 1-3). Analysis of neutral beam scattering profiles and collisionally reionized mass spectra for NH4(NH3) and ND4(ND3) indicate that these clusters are formed in a distribution of metastable and dissociative states. The n = 1 cluster in its dissociative state has sufficient internal energy to break up to 2NH3 + H without formation of the dimer (NH3)2. The species N2D6H decomposes by preferential loss of a H atom analogous to the dissociative behavior of ND3H. The lifetimes of the metastable states of NH4(NH3) and ND4(ND3) are greater than 1 μs. From thermodynamic considerations the ionization potential of NH4(NH3) is estimated to be 4.0 ± 0.2 eV. As n increases, the ionization potentials for the clusters decrease to a value of about 2.5 eV for NH4(NH3)3. Spectroscopic considerations suggest that NH4(NH3) and ND4(ND3) will exhibit an electronic absorption spectrum involving low-lying Rydberg states.

UR - http://www.scopus.com/inward/record.url?scp=0000177472&partnerID=8YFLogxK

U2 - 10.1021/j150670a035

DO - 10.1021/j150670a035

M3 - Article

AN - SCOPUS:0000177472

SN - 0022-3654

VL - 88

SP - 6680

EP - 6684

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 26

ER -

An experimental study of hypervalent molecular clusters by neutralized ion beam spectroscopy: NH₄(NH₃)_n and ND₄(ND₃)_n for n = 1-3

Abstract

Access to Document

Other files and links

Fingerprint

Cite this