Steric effects on nascent vibrational distributions of the HCN product produced in CN radical reactions with ethane, propane and chloroform

Morris, Vernon R.; Mohammad, Fida; Valdry, Lynnette; Jackson, William M.

doi:10.1016/0009-2614(94)00212-6

Cited by 24 publications

(30 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…15,16 In order to unravel the influence of the solvent on the reaction it is useful to compare our studies in solution with those of the well-characterized solvent-free dynamics of CN + RH reactions in the gas phase. 17,18,19,20,21,22 These studies show that HCN is formed with substantial vibrational excitation in both the C−H stretch and bending modes. For the reactions of CN radicals with a range of small organic molecules (methane, ethane, propane, cyclopropane, isobutane, neopentane and chloroform), Jackson and co-workers reported that up to 2 quanta of C−H stretch are excited and a population inversion is observed between the v 3 =2 and v 3 =1 vibrational levels for all except the reactions with methane and cyclopropane.…”

Section: Many Reactions Of Biological and Chemical Importance Occur Imentioning

confidence: 87%

“…For the reactions of CN radicals with a range of small organic molecules (methane, ethane, propane, cyclopropane, isobutane, neopentane and chloroform), Jackson and co-workers reported that up to 2 quanta of C−H stretch are excited and a population inversion is observed between the v 3 =2 and v 3 =1 vibrational levels for all except the reactions with methane and cyclopropane. 19,22 Complementary experiments led Macdonald and coworkers to conclude that almost every (>99%) HCN product of the reaction of CN with ethane is formed with the bending vibrational mode excited above its zero-point level. 18 However, excited levels of the C≡N stretching mode…”

Section: Many Reactions Of Biological and Chemical Importance Occur Imentioning

confidence: 99%

See 1 more Smart Citation

Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution

Rose

Greaves

Oliver

et al. 2011

The Journal of Chemical Physics

View full text Add to dashboard Cite

Link to publication record in Explore Bristol Research PDF-documentThe following article has been submitted to/accepted by Journal of Chemical Physics. After it is published, it will be found at 10.1063/1.3603966 University of Bristol -Explore Bristol Research General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above.

show abstract

Section: Many Reactions Of Biological and Chemical Importance Occur Imentioning

confidence: 87%

Section: Many Reactions Of Biological and Chemical Importance Occur Imentioning

confidence: 99%

Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution

Rose

Greaves

Oliver

et al. 2011

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Ultraviolet photolysis of ICN in solution in CDCl 3 revealed that ~20% of the DCN products of the reaction of CN radicals with CDCl 3 were formed with one quantum of excitation of the C−D stretching mode, but for equivalent experiments in CHCl 3 , only vibrationally ground state HCN was observed. 7,11 These reactions are known to produce highly vibrationally excited products under isolated collision conditions, 12,13,14,15,16 and the conclusion was drawn that the solvent modifies the reaction energy landscape to suppress vibrational energy release. In more recent investigations, Crim and co-workers observed both the rates of removal of CN radicals and production of HCN in reactions with various organic species in a range of chlorinated solvents, using, respectively, transient visible and IR absorption spectroscopy.…”

mentioning

confidence: 99%

Chemical Reaction Dynamics in Liquid Solutions

Orr-Ewing

Glowacki

Greaves

et al. 2011

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

The dynamics of bimolecular chemical reactions can be examined in liquid solutions using infra-red absorption spectroscopy with picosecond time resolution. On such short timescales, the transient absorption spectra reveal vibrational mode and quantum-state specific energy disposal, followed by vibrational relaxation as the energy is dissipated to the surrounding solvent. Comparison with energy disposal measurements for gas-phase reactions under single-collision conditions offers direct insights into the modification of the energy landscape and the nuclear dynamics in the presence of the solvent. The reactions of CN radicals with organic molecules in chlorinated solvents exemplify the dynamical information that can be obtained. The potential to extend such experiments to a range of reactions and solvents is discussed. TOC graphic

show abstract

“…These two first-order rate coefficients relate to the bimolecular rate coefficients for reactions (9) and (10) via: …”

Section: Effect Of Adding Methanol On Hcn Formation In Acetonitrile 17mentioning

confidence: 99%

“…4,5 These reactive radicals typically abstract hydrogen atoms from organic molecules as shown by Equation (1), and the reactions with alkanes have been extensively studied in the gas phase. [9][10][11][12][13][14] CN + RH → HCN(v1,v2,v3) + R…”

Section: Introductionmentioning

confidence: 99%

Reaction Dynamics of CN Radicals in Acetonitrile Solutions

et al. 2015

View full text Add to dashboard Cite

General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms Time-resolved electronic absorption spectroscopy (TEAS) in the ultraviolet and visible spectral regions observes rapid production and loss (with a decay time constant of 0.6  0.1 ps) of the photolytically generated free CN radicals. Some of these radicals convert to a solvated form which decays with a lifetime of 8.5  2.1 ps. Time-resolved vibrational absorption spectroscopy (TVAS) reveals that the free and solvated CN-radicals undergo geminate recombination with I atoms to make ICN and INC, H-atom abstraction reactions, and addition reactions to solvent molecules to make C3H3N2 radical species. These radical products have a characteristic absorption band at 2036 cm -1 that shifts to 2010 cm -1 when ICN is photolysed in CD3CN. The HCN yield is low, suggesting the addition pathway competes effectively with Hatom abstraction from CH3CN, but the delayed growth of the C3H3N2 radical band is best described by reaction of solvated CN radicals through an unobserved intermediate species.Addition of methanol or tetrahydrofuran as a co-solute promotes H-atom abstraction reactions that produce vibrationally hot HCN. The combination of TEAS and TVAS measurements shows that the rate-limiting process for production of ground-state HCN is vibrational cooling, the rate of which is accelerated by the presence of methanol or tetrahydrofuran.

show abstract

Steric effects on nascent vibrational distributions of the HCN product produced in CN radical reactions with ethane, propane and chloroform

Cited by 24 publications

References 23 publications

Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution

Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution

Chemical Reaction Dynamics in Liquid Solutions

Reaction Dynamics of CN Radicals in Acetonitrile Solutions

Contact Info

Product

Resources

About