Theoretical study of the OH+NO2 reaction: formation of nitric acid and the hydroperoxyl radical

Chakraborty, Debajit; Park, Jeanie; Lin, Ming‐Chang

doi:10.1016/s0301-0104(98)00033-0

Cited by 51 publications

(66 citation statements)

References 40 publications

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“…A kinetically important transition state would need to be near or below the dissociation energy for HONO 2 ; this work assumes the HONO 2 and HOONO wells do not communicate. Various calculations and experiments have confirmed there is no intrinsic energy barrier for the formation of HONO 2 or HOONO from the reactants [6,12].…”

Section: Overviewmentioning

confidence: 98%

“…The value of ⌬E 0 0 for HONO 2 (47.7 kcal/mol) is taken from the experimental dissociation energy cited in [12]. Sumathi and Peyerimhoff have calculated a transition state for the isomerization of HONO 2 to HOONO, but the barrier height they found is well above the dissociation limit for HONO 2 [18].…”

Section: Overviewmentioning

confidence: 99%

“…Global atmospheric models have proved particularly sensitive to k 1 [1,2], and the importance of this reaction has inspired numerous experimental studies [5 -11]. In ad-dition, Chakraborty and coworkers recently performed a canonical variational transition state theory (CVTST) estimation of the high-pressure rate constant k 1 ϱ at [cm 3 /mol/s] [12]. The recent 13 300 K (3.31 ϫ 10 work of Donahue et al and Dransfield et al [5,11] has led to proposed changes in the IUPAC and JPL recommendations [13,14] for k 1 , through incorporation of the full Troe falloff parameterization [15].…”

Section: Introductionmentioning

confidence: 99%

“…In addition to experimental work, various authors have performed ab initio or other calculations on OH, NO 2 , HONO 2 , and HOONO [12,16,18 -22]. Chakraborty and coworkers studied the OH ϩ NO : 2 surface [12]. Sumathi and Peyerimhoff pre-HONO 2 pared a detailed energy surface including all the species in the present work [18], which allows us to make a more detailed analysis of the HOONO channel than has been done previously.…”

Section: Introductionmentioning

confidence: 99%

“…We use the inverse Laplace transform approach (ILT) [24 -28] and both the modified strong collision (MSC) [36] and master equation (MEQ) treatments of collisional deactivation. The ILT approach was chosen because of its particular usefulness in reactions with no barrier to recombination, and because it requires no explicit information about the transition state [12,24]. We explore the sensitivity of the rate constant predictions for (1) to collisional energy transfer parameters, well depth, high-pressure rate constant value, treatment of OH moieties (in HOONO and HONO 2 ) as stiff vibrators, hindered rotors, or free rotors, and the inclusion or exclusion of "adiabatic" external rotational modes.…”

Section: Introductionmentioning

confidence: 99%

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A priori falloff analysis for OH + NO2

Matheu

Green

2000

Int. J. Chem. Kinet.

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The pressure-dependent rate constants for the recombination of hydroxyl radical and nitrogen dioxide to form nitric acid and peroxynitrous acid k 1 (OH ϩ NO 9 9 : HONO ) 2 2 are calculated a priori using two inverse Laplace transform ap-(OH ϩ NO 9 9 : HOONO) 2 proaches and both the modified strong collision and the master equation treatments of collisional energy transfer, at a variety of temperatures and pressures. Accuracy within a factor of 3 is demonstrated for the most accurate a priori predictions of k 1 . The estimate of k 1 at ambient conditions was not very sensitive to uncertainties in the barrier height (dissociation limit), the average collisional energy transferred ͗⌬E down ͘, the high-pressure limit k 1 ϱ , or to treatments of the OH torsions as stiff vibrators, hindered rotors, or free rotors. Estimates of k 1 were sensitive to coupling between the reaction coordinate and the external rotational mode, or J mode, of the adduct. Increased accuracy in any further a priori calculation of k 1 or k 2 depends on improvements to the treatment of the J mode. We calculate the equilibrium constant for the formation of HOONO from OH and NO 2 , treating the OH moiety as a hindered rotor and using a direct-count density of states algorithm, to be K ϭ 1.3 ϫ OHϩNO : HOONO 2

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Section: Overviewmentioning

confidence: 98%

Section: Overviewmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A priori falloff analysis for OH + NO2

Matheu

Green

2000

Int. J. Chem. Kinet.

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Analysis of the temperature and pressure dependence of the reaction HO + NO₂+ M ⇔︁ HONO₂+ M

Troe¹

2001

Int J of Chemical Kinetics

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A theoretical analysis of the temperature and pressure dependence of the reaction HO + NO 2 + M ⇔ HONO 2 + M is made over the temperature range 50-1400 K and the pressure range 10 −4 -10 3 bar where experimental data are available. The treatment accounts for contributions from anharmonicity, centrifugal barriers, angular momentum couplings, and weak collisions. It is shown that broadening factors F(x ), with log F( (T /300 K) −3.0 cm 6 molecule −2 s −1 and k 1,∞ = 3.6 × 10 −11 cm 3 molecule −1 s −1 , are consistent with experiments over the range 220-400 K. The NASA/JPL policy of using F c = 0.6 and N = 1 leads to apparent values of k 1,0 , and k 1,∞ which are too low, although experimentally observed parts of the falloff curves can well be reproduced. The IUPAC recommendation of a temperature dependence of F c ≈ exp(−T /T c ) should also be abandoned because F c is nearly temperature independent between 50 and 1400 K. The analysis of experimental limiting low pressure rate coefficients k 1,0 leads to apparent average energies E transferred per collision of about −160 cm −1 for M = N 2 , and −80 cm −1 for M = Ar, which are nearly temperature independent over the range 200-400 K for M = N 2 , and only weakly temperature dependent between 300 and 1400 K for M = Ar. The analysis of k 1,0 , which leads to E , and of k 1,∞ , however, are markedly influenced by the lack of sufficiently precise information on the interaction potential between HO and NO 2 . For this reason, the consequences of uncertainties are discussed in detail. Possible contributions of HOONO isomer formation in the reaction are also discussed. It is shown that HOONO yields, at pressures below 1 bar, most probably are smaller than about 2.5% while yields up to 20% are possible at 100 bar.

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Coupled‐cluster studies of HOONO⁺: Additional conformers of the ²A″ON⁺OOH complex and a comparison of restricted and unrestricted open‐shell Hartree–Fock coupled‐cluster results

Watts

Francisco

2004

Int J of Quantum Chemistry

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Coupled-cluster calculations using the CCSD(T) method (coupledcluster singles and doubles with perturbative inclusion of triple excitations) and correlation-consistent basis sets have been used to address aspects of the lowest 2 AЈ and 2 AЉ potential energy surfaces of the peroxynitrous acid cation (HOONO ϩ ). First, searches were made for conformers of the 2 AЉ ON ϩ OOOH complex in addition to the cis-trans species previously located by the authors (J Chem Phys 2003, 118, 1721. Two conformers were located-namely, trans-cis and trans-trans species-and these were confirmed to be local minima. The trans-trans conformer was calculated to be less than 0.5 kcal mol Ϫ1 higher in energy than the cis-trans conformer, and the trans-cis conformer was calculated to be about 6.4 kcal mol Ϫ1 higher in energy than the cis-trans conformer. Second, comparisons were made between CCSD(T) results obtained with unrestricted Hartree-Fock (UHF) and restricted open-shell Hartree-Fock (ROHF) reference determinants. These comparisons were made on the 2 AЉ complexes and the planar 2 AЈ HOONO ϩ stationary points. In general, the energy differences between UHF-CCSD(T) and ROHF-CCSD(T) were very small, and well within the error bars of the methods.

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Theoretical study of the OH+NO2 reaction: formation of nitric acid and the hydroperoxyl radical

Cited by 51 publications

References 40 publications

A priori falloff analysis for OH + NO2

A priori falloff analysis for OH + NO2

Analysis of the temperature and pressure dependence of the reaction HO + NO₂+ M ⇔︁ HONO₂+ M

Coupled‐cluster studies of HOONO⁺: Additional conformers of the ²A″ON⁺OOH complex and a comparison of restricted and unrestricted open‐shell Hartree–Fock coupled‐cluster results

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Theoretical study of the OH+NO2 reaction: formation of nitric acid and the hydroperoxyl radical

Cited by 51 publications

References 40 publications

A priori falloff analysis for OH + NO2

A priori falloff analysis for OH + NO2

Analysis of the temperature and pressure dependence of the reaction HO + NO2+ M ⇔︁ HONO2+ M

Coupled‐cluster studies of HOONO+: Additional conformers of the 2A″ON+OOH complex and a comparison of restricted and unrestricted open‐shell Hartree–Fock coupled‐cluster results

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Analysis of the temperature and pressure dependence of the reaction HO + NO₂+ M ⇔︁ HONO₂+ M

Coupled‐cluster studies of HOONO⁺: Additional conformers of the ²A″ON⁺OOH complex and a comparison of restricted and unrestricted open‐shell Hartree–Fock coupled‐cluster results