Photoabsorption spectra of gaseous CF3NO, CCI3NO, and CCI3NO2

Allston, Thomas D; Fedyk, M.L.; Takacs, G. A.

doi:10.1016/0009-2614(78)85719-4

Cited by 24 publications

(7 citation statements)

References 30 publications

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“…No pressure dependence was found for reaction 6, which is in agreement with our previous study. 23 The optimized absorption cross sections for CCI3NO, even under conditions where a significant fraction of the CC13 radicals react via reaction 6, are in good agreement with the room temperature measurement of Allston et al,25 giving us further confidence in the results. The closed symbols on the fall-off curves in Figure 3 represent the data obtained in these high-pressure measurements.…”

Section: Resultssupporting

confidence: 76%

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Kinetics and thermochemistry of the reaction: trichloromethyl + nitric oxide + M .dblarw. trichloronitrosomethane + M

Masanet¹,

Caralp²,

Jemi-Alade³

et al. 1993

J. Phys. Chem.

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The kinetics and equilibrium constant of reaction 1, CCI, + N O + M -CC13N0 + M, were investigated using pulsed-laser photolysis/time-resolved mass spectrometry at low pressure, 0.5-1 2 Torr, and flash-photolysis/UV absorption spectrometry at high pressure, 110-760 Torr. These pressure ranges cover most of the fall-off region. Fall-off curves were measured at 263, 298, and 373 K and a determination of the rate constant was performed at 465 K, 760 Torr. RRKM calculations were performed for accurate extrapolation to the low and high pressure limits. The rate expressions obtained are, using the formalism of Troe, k1 (0) = [(1.4 f 0.3) X 10-29](T/298 K)(-5~5i0.2)cm6molecule-2s-~ and k l ( m ) = [(7.5 i 1.5) X 10-I2](T/298 K)(-1.0*0.3)cm3 molecule-' s-I, with Fc = 0.66 exp(-T/600 K). The collisional efficiency factor 8, = (0.43 f 0.04)(T/298)(-1.0*0.2) is reasonable, thereby establishing the consistency between kinetic and thermochemical data. The rate expression at 760 Torr is kl(760 Torr) = [(5.2 f 1.0) X 10-'2](T/298)-(2.65i0.2) cm3 molecule-l s-I. The equilibrium constant was measured at 480 and 486 K and the entropy of reaction was calculated using statistical thermodynamics, with the purpose of determining the enthalpy of reaction: L$H0298 = -125 i 8.5 kJ mol-I. This value, corresponding to the bond dissociation energy D(CCl,-NO), is significantly smaller than the corresponding bond dissociation energies in CH3NO and in CF3NO: 172 and 167 kJ mol-', respectively. Ab initio calculations of the above bond dissociation energies have yielded values in good agreement with experimental data.

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Section: Resultssupporting

confidence: 76%

“…At this wavelength, the absorption cross section of CC13 is 9.9 X 10-18 cm2 molecule-1,23 and that of CCI3NO is 1.2 X10-18 cm2 molecule-1 at room temperature. 25 The large difference between these values allowed the conversion of CC13 into CCl3NO to be easily monitored by UV absorption.…”

Section: Resultsmentioning

confidence: 99%

Kinetics and thermochemistry of the reaction: trichloromethyl + nitric oxide + M .dblarw. trichloronitrosomethane + M

Masanet¹,

Caralp²,

Jemi-Alade³

et al. 1993

J. Phys. Chem.

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“…Chloropicrin is an agricultural pesticide that can escape into the atmosphere after application, 22 and its primary environmental removal pathway is photolysis. 23 Because of the similarity of its ultraviolet spectrum to that of nitromethane, 24 it might be reasonable to predict that chloropicrin's photolysis mechanism would be comparable to that of nitromethane. However, the earliest study of the environmental removal of chloropicrin, by Moilanen et al, 25 suggested that chloropicrin did not photolyze in the absence of oxygen.…”

Section: Introductionmentioning

confidence: 99%

Time-Dependent Infrared Emission Following Photodissociation of Nitromethane and Chloropicrin

Wade¹,

Reak²,

Li³

et al. 2006

J. Phys. Chem. A

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Nitromethane (CH(3)NO(2)) and its chlorinated analogue, chloropicrin (CCl(3)NO(2)), were photolyzed at 193, 248, and 266 nm, and the products were observed by time-dependent Fourier transform infrared emission spectroscopy. At 193 and 248 nm, the primary photodissociation pathway for nitromethane was cleavage of the C-N bond to produce CH(3) + NO(2)(A (2)B(2)). At 266 nm, weak emission was observed following photodissociation of nitromethane, but an infrared spectrum could not be obtained. The photodissociation of chloropicrin at 193 nm produced the analogous product channel CCl(3) + NO(2)(A (2)B(2)) in addition to several other product channels. At 248 and 266 nm, only CCl(3) + NO(2)(A (2)B(2)) was observed. The production of phosgene (CCl(2)O) from chloropicrin photodissociation was not observed in this study.

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“… e Vertical MR-CI/6-31G(d)+ spd //B3LYP/6-31G(d) f Experimental λ max in gas phase at 295 K g Experimental λ max in CCl 4 …”

Section: Resultsmentioning

confidence: 99%

Calculations of n→π* Transition Energies: Comparisons Between TD-DFT, ADC, CC, CASPT2, and BSE/GW Descriptions

et al. 2017

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Using a large panel of theoretical approaches, namely, CC2, CCSD, CCSDR(3), CC3, ADC(2), ADC(3), CASPT2, time-dependent density functional theory (TD-DFT), and BSE/evGW, the two latter combined with different exchange-correlation functionals, we investigate the lowest singlet transition in 23 n→π* compounds based on the nitroso, thiocarbonyl, carbonyl, and diazo chromophores. First, for 16 small derivatives we compare the transition energies provided by the different wave function approaches to define theoretical best estimates. For this set, it surprisingly turned out that ADC(2) offers a better match with CC3 than ADC(3). Next, we use 10 functionals belonging to the "LYP" and "M06" families and compare the TD-DFT and the BSE/evGW descriptions. The BSE/evGW results are less sensitive than their TD-DFT counterparts to the selected functional, especially in the M06 series. Nevertheless, BSE/evGW delivers larger errors than TD-CAM-B3LYP, which provides extremely accurate results in the present case, especially when the Tamm-Dancoff approximation is applied. In addition, we show that, among the different starting points for BSE/evGW calculations, M06-2X eigenstates stand as the most appropriate. Finally, we confirm that the trends observed on the small compounds pertain in larger molecules.

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Photoabsorption spectra of gaseous CF3NO, CCI3NO, and CCI3NO2

Cited by 24 publications

References 30 publications

Kinetics and thermochemistry of the reaction: trichloromethyl + nitric oxide + M .dblarw. trichloronitrosomethane + M

Kinetics and thermochemistry of the reaction: trichloromethyl + nitric oxide + M .dblarw. trichloronitrosomethane + M

Time-Dependent Infrared Emission Following Photodissociation of Nitromethane and Chloropicrin

Calculations of n→π* Transition Energies: Comparisons Between TD-DFT, ADC, CC, CASPT2, and BSE/GW Descriptions

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