Matrix Isolation and Cold Diffusion of Mass-Selected CS2•+ in Neon:  Infrared Observation of the Asymmetric Stretch of CS2•+ and CS2•-

Halasinski, Thomas M.; Godbout, Jerry T.; Allison, and John; Leroi, G. E.

doi:10.1021/jp960862f

Cited by 18 publications

(12 citation statements)

References 28 publications

(41 reference statements)

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“…Within the combined experimental error, three neonmatrix absorptions observed in the present study correspond in frequency to those reported by Halasinski and co-workers 38 and, with reassignment to (CO 2 ) 2…”

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confidence: 91%

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The vibrational spectra of CO2+, (CO2)2+, CO2−, and (CO2)2− trapped in solid neon

Thompson

Jacox

1999

The Journal of Chemical Physics

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When a Ne:CO2 mixture is subjected to Penning ionization and/or photoionization by neon atoms in their first excited states, between 16.6 and 16.85 eV, and the products are rapidly frozen at approximately 5 K, the infrared spectrum of the resulting deposit includes absorptions assigned to CO2+, (CO2)2+, CO2−, and (CO2)2−. The lowest (μ 2∑u+) Renner component of the bending fundamental of CO2+ trapped in a neon matrix appears near the gas-phase band center, but other Renner components are undetectable. Absorptions of a photolabile product correspond to the recently identified CO-stretching fundamentals of (CO2)2+. Weak infrared absorptions at 1253.8 and 714.2 cm−1 are assigned to ν1 and ν2 of CO2−, respectively, and a moderately intense absorption at 2894.7 cm−1 is assigned to the ν1+ν3 combination band of that product. As in other recent argon- and neon-matrix studies, two weak infrared absorptions can be assigned to the two infrared-active OCO-stretching fundamentals of the D2d structure of (CO2)2−. Detailed isotopic substitution studies support all of these assignments. A weak absorption near the CO2 bending fundamental, for which isotopic substitution data are incomplete, may be contributed either by a second fundamental of (CO2)2− (D2d) with b2 symmetry or by a weakly interacting (CO2)n⋅⋅CO2− complex. Such ion–molecule complexes contribute other absorptions near ν3 of CO2 and of CO2−.

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confidence: 91%

“…Halasinki and co-workers 38 reported the infrared spectrum of species present in a mass-selected beam formed by the ionization of a Ne:CS 2 :CO 2 mixture and trapped in a neon matrix. In this system, CO 2 served as an electron captor.…”

mentioning

confidence: 99%

The vibrational spectra of CO2+, (CO2)2+, CO2−, and (CO2)2− trapped in solid neon

Thompson

Jacox

1999

The Journal of Chemical Physics

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“…These bands have essentially the same isotopic ratios and are suitable for assignment to the antisymmetric vibration of the CO 2 Ϫ anion. Ϫ in solid neon [17][18][19] and the 1671 cm Ϫ1 value in alkali halide discs. 16 Furthermore, the concentration studies suggest that the 1652.7 cm Ϫ1 band might involve two coordinating CO 2 submolecules.…”

Section: Resultsmentioning

confidence: 99%

“…1,2 More recently, Jacox and Thompson assigned an infrared absorption at 1658.3 cm Ϫ1 to the CO 2 Ϫ anion isolated in a neon matrix, 17 and CO 2 Ϫ was observed at 1658.5 cm Ϫ1 as a counterion in neon matrix mass-selected cation beam experiments. 18,19 In addition Knight and co-workers reported electron spin resonance studies of the CO 2 Ϫ anion in rare-gas matrices, which was generated by four different methods. 20 Carbon dioxide cluster anions can be prepared by lowenergy electron attachment onto (CO 2 ) n neutral clusters formed in supersonic expansion.…”

Section: Introductionmentioning

confidence: 99%

Infrared spectra of the CO2− and C2O4− anions isolated in solid argon

Zhou

Andrews

1999

The Journal of Chemical Physics

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IR spectroscopy on isolated Co n ( alcohol ) m cluster anions ( n = 1 -4 , m = 1 -3 ) : Structures and spin states Structures of [ ( C O 2 ) n ( H 2 O ) m ] − ( n = 1 -4 , m = 1 ,2) cluster anions. I. Infrared photodissociation spectroscopy J. Chem. Phys. 122, 094303 (2005); 10.1063/1.1850896 Spectroscopic identification of the CO-H 2 O 2-1 cluster trapped in an argon matrixLaser ablation of transition metal targets with concurrent 11 to 12 K condensation of CO 2 -Ar mixtures produces a sharp metal independent infrared absorption at 1657.0 cm Ϫ1 due to CO 2 Ϫ , which is formed from the capture of ablated electrons by CO 2 molecules during the condensation process. Two additional metal independent absorptions are produced at 1856.7 and 1184.7 cm Ϫ1 on matrix annealing to 25 K to allow diffusion and reaction of CO 2 and CO 2 Ϫ . Isotopic substitution ( 13 CO 2 , C 18 O 2 , C 16,18 O 2 , and mixtures͒ shows that these two vibrations involve two equivalent CO 2 subunits. The excellent agreement with frequencies, intensities, and isotopic frequency ratios from density-functional calculations supports assignment to the symmetrical C 2 O 4Ϫ anion with D 2d symmetry. Photodissociation ͑470-580 nm͒ and failure to observe these absorptions in identical experiments doped with the electron trapping molecule CCl 4 further support the molecular anion assignments. Although absorptions were observed for weak ͑CO 2 ͒͑CO 2 Ϫ ͒ complexes, no evidence was found for the asymmetric O 2 C•OCO Ϫ molecule-anion complex characterized by calculations.

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“…John Allison and George Leroi (then) from the Department of Chemistry at Michigan State University. [23][24][25][26] Since many modifications have been made, a complete description is provided here.…”

Section: Methodsmentioning

confidence: 99%

Infrared spectroscopic characterization of hydrogen-bonded propylene oxide − ethanol and propylene oxide − 2-fluoroethanol complexes isolated in solid neon matrices

2013

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The infrared absorption spectra of hydrogen-bonded complexes of propylene oxide with either ethanol or 2-fluoroethanol have been recorded in neon matrices. Mixtures of propylene oxide and ethanol or propylene oxide and 2-fluoroethanol vapors were mixed with an excess of neon gas and deposited onto a KBr substrate at 4.2 K. The results indicate that hydrogen-bonded complexes were formed with propylene oxide as the hydrogen bond acceptor and either ethanol or 2-fluoroethanol as the hydrogen bond donors. The features assigned to the O−H stretch were red-shifted by 175 and 193 cm −1 for the ethanol-and 2-fluoroethanol-containing complexes, respectively. The difference in red shifts can be accounted for due to the greater acidity of 2-fluroethanol. Deuterium isotope experiments were conducted to help confirm the assignment of the O-H stretch for the complexes. As well, structures and infrared spectra were calculated using B3LYP/6-311++G(2d,2p) calculations and were used to compare with the experimental spectra. A "scaling equation" rather than a scaling factor was used and is shown to greatly increase the utility of the calculations when comparing with experimental spectra. An examination of the O-H stretching red shifts for many hydrogen-bound complexes reveals a relationship between the shift and the difference between the acidity of the hydrogen bond donor and the basicity of the hydrogen bond acceptor (the enthalpy of proton transfer). Both hydrogen-bonded complexes and proton-bound complexes appear to have a maximum in the reduced frequency value that corresponds to complexes where the hydrogen/proton are equally shared between the two bases.

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Matrix Isolation and Cold Diffusion of Mass-Selected CS₂^•+ in Neon: Infrared Observation of the Asymmetric Stretch of CS₂^•+ and CS₂^•-

Cited by 18 publications

References 28 publications

The vibrational spectra of CO2+, (CO2)2+, CO2−, and (CO2)2− trapped in solid neon

The vibrational spectra of CO2+, (CO2)2+, CO2−, and (CO2)2− trapped in solid neon

Infrared spectra of the CO2− and C2O4− anions isolated in solid argon

Infrared spectroscopic characterization of hydrogen-bonded propylene oxide − ethanol and propylene oxide − 2-fluoroethanol complexes isolated in solid neon matrices

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