Theoretical Study on the Reaction of Nitric Oxide with Propargyl

Subscriber access provided by ECU Libraries

A: Kinetics, Dynamics, Photochemistry, and Excited States

Theoretical Study on the Reaction of Nitric Oxide with Propargyl Radical Xiaowen Wang, Jinou Song, Gang Lv, and Zhijun Li J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.8b11771 • Publication Date (Web): 15 Jan 2019 Downloaded from http://pubs.acs.org on January 16, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

Theoretical Study on the Reaction of Nitric Oxide with Propargyl Radical Xiaowen Wang, Jinou Song*, Gang Lv, Zhijun Li State Key Laboratory of Engines, Tianjin University, Tianjin, China

ABSTRACT The reaction of nitric oxide (NO) with propargyl radical (C3H3) was investigated at the CCSD(T)/cc-pVTZ//B3LYP/6–311++G(df, pd) level of theory. The rate coefficients of the system were determined using RRKM – CVT method with Eckart tunneling correction over a temperature range of 200 - 800 K and a pressure range of 1.0 × 10-4 – 10.0 bar. Eight channels proceeding via the barrierless formation of excited intermediate ONCH2CCH or CH2CCHNO at the first step were explored. Three favorable channels (i.e. channels producing adduct of ONCH2CCH and CH2CCHNO and products of HCN and H2CCO) were confirmed. The rate coefficients of channels producing adduct of ONCH2CCH and CH2CCHNO are comparable and have weak negative temperature dependence and positive pressure dependence. Channel producing products of HCN and H2CCO is more important at low pressure and high temperature and less important after pressure greater than 1.0 × 10-2 bar (with a branching ratio less than 6% at 0.1 bar).

Corresponding author. E-mail address: [email protected] *

1

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 20

1. Introduction Nitric oxide (NO) as a combustion product can react with several hydrocarbon radicals1-4. Among these radicals, propargyl radical (C3H3) has been proposed as critical intermediates in hydrocarbon reaction systems pertinent to both low temperatures of planetary atmospheres and high temperatures of combustion systems5–7, since it has been widely proposed to play a major role in the formation of the aromatic rings via the self-reaction in the combustion system and can accumulate in relatively high concentrations in flame because of its resonantly stabilized structure 8-22.

For the propargyl radical reactions, both of the resonant structures acetylenic

hybrid (HC≡C−CH2) and allenic hybrid (HC=C=CH2) were taken into consideration, such as C3H3 reaction with O (3P)11, O2 12-13, C (3Pj)19, CH320, allyl (C3H5)21, benzyl (C7H7)22. The reaction between C3H3 and NO could have an impact on several aspects of combustion chemistry. DeSain et al 16 measured the C3H3 + NO reaction rate over the temperature range of 195 - 473 K and the pressure range of 3 - 100 Torr using a color center laser infrared kinetic spectroscopy, and determined the enthalpy changes for

the

adducts

of

ONCH2CCH

and

CH2CCHNO

by

performing

both

B3LYP/6-311++G(2df,2pd) and G2 calculations. However, the further kinetic information on the reaction of C3H3 +NO, such as rate coefficients, product channels and their branching ratios, has not been well understood. In the present work the essential features of the potential energy surface (PES) of the title reaction are investigated at a reliable computational level and new product channels and rate coefficients of the reaction are determined. 2


Page 3 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2. Computational methods The geometries and energies calculations of the stationary points along the minimum energy paths (MEPs) were performed using the Gaussian0923 program package. The structures of the reactants, products, intermediates, and transition states related to the reaction were optimized employing both the B3LYP24-26 and M06-2X27-29 methods with the 6-311++G(df,pd) basis set, respectively. Harmonic frequencies were used to identify the structures for a local minima with all real frequencies or a saddle transition state with only one imaginary frequency and zero-point energy (ZPE) corrections were also obtained simultaneously. The results were scaled by a factor of 0.9830. Subsequently, intrinsic reaction coordinate (IRC)31-32 calculations were performed at the same level to confirm every transition state connecting to the right reactants and products. To facilitate the accuracy of the reaction energies on the PES, the

high-level

CCSD(T)/aug-cc-pVTZ

//

B3LYP/6-311++G(df,pd),

CCSD(T)/cc-pVTZ // B3LYP/6-311++G(df,pd)33, and G434 single-point energy calculations (based on the optimized geometries at the B3LYP/6-31G(2df, p) level of the theory) were implemented. The reaction rate coefficients and branching ratios were computed over a temperature range of 200 - 800 K and a pressure range of 1.0 × 10-4 – 10.0 bar with the Mesmer program35 based on canonical variational transition state theory (CVT)36-38 and Rice−Ramsperger−Kassell−Marcus (RRKM) theory39, which has been successfully employed to calculate the individual rate coefficient in the presence of the other channels in multiwell reaction systems40-42. One-dimensional asymmetric Eckart 3



Page 4 of 20

tunneling corrections43 were also included.

3. Results and discussion 3.1 Potential energy surface and reaction mechanism Figure S1 (Supporting information) depicts the optimized geometries of the reactants, products,

intermediates

and

transition

states

for

the

title

reaction

at

B3LYP/6-311++G(df,pd) and M06-2X/6-311++G(df,pd) levels of theory along with the available reference data. The structures calculated in this work compare well with experimental results in the literature30 for NO, HCCH and HCNO, and compare well with the calculated results in the literature44 for C3H3, in the literature45 for H2CC, in the literature46 for HOCN and HONC, and in the literature16 for ONCH2CCH (denoted as IM1) and CH2CCHNO (denoted as IM2). The maximum deviations of all the bond length and bond angle are less than 0.034 Å and 0.9 ° at B3LYP/6-311++G(df,pd) level, and 0.035 Å and 2.4 ° at M06-2X/6-311++G(df,pd) level. Table S1 (Supporting information) lists the harmonic vibrational frequencies and ZPE corrections calculated with B3LYP method accompanied by the corresponding experimental values30. Note that the theoretical results are in great agreement with the experimental data, the average deviations between them generally less than 4%. The character of each transition state is confirmed by normal mode analysis, which yields only one imaginary frequency whose eigenvector corresponds to the direction of each reaction. The T1-diagnostic has also been performed for all the stationary points at the 4


Page 5 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


CCSD(T)/cc-pVTZ level of the theory to evaluate the multi-reference character. The T1 values of all intermediate species and transition states in the title reaction are smaller than the threshold value of 0.04547, indicating that the single-reference method gives an adequate description of the wave function. Table 1 exhibits relative energies (ΔE (0 K)) and the relative enthalpies (ΔH (298 K)) for all stationary points at CCSD(T)/aug-cc-pVTZ, CCSD(T)/cc-pVTZ and G4 levels of the theory and the corresponding reaction enthalpies evaluated based on the reference data given in Table S2 (Supporting information). Considering the uncertainties in the calculated ΔH values (∼1.0 kcal/ mol) and the Δf H0298 values as given in Table S2 (Supporting information), the four sets of data exhibit general consensus. In addition, the calculated results of IM1 and IM2 in this work are comparable with the calculated results in the work of De Sain et al 16. Figure

1

shows

the

PES

for

the

system

of

C3H3

+

NO

at

the

CCSD(T)/cc-pVTZ//B3LYP/6-311++G(df,pd) level of theory, and the relative energy of the system of C3H3 + NO is set to 0 for reference. For the entrance attack of NO to C3H3, the optimizations of the O attack and NO-π-bond attack always failed, and no H abstraction channels were found. Only is the N attack kinetically feasible. As N attacks C3H3 to form IM1 and IM2 barrierlessly, there is no explicit transition state (Figure S2, Supporting Information) for the entrance channels. IM2 can interconvert with IM1 through TS1-2 with a barrier height of 4.6 kcal/mol, or produce products HCN and H2CCO through TS2-3, IM3 and TS3-P1. The barrier heights of TS2-3 (-0.7 kcal/mol) and TS1-2 (4.6 kcal/mol) are far lower than those of TS1-4 (23.4 kcal/mol), 5



Page 6 of 20

TS2-5 (26.5 kcal/mol) and TS2-7 (29.1 kcal/mol), indicating that the channels through those transition states are kinetically favorable. Therefore, the mechanism of the reaction of C3H3 + NO can be depicted in Scheme 1. Scheme 1. Mechanism of the reaction of C3H3 + NO C3H3 + NO

IM1*

R1 IM1

Rw1

IM2

R12

IM2*

R2 IM2

Rw2

IM1

R21

IM3*

R3 IM3 P1

Rw3 Rp1

where ‘‘*” represents the vibrational excitation of the intermediates. 3.2 Rate coefficients calculation For barrierless entrance channels shown in Schemes 1, the calculation of the rate coefficients were carried out by a canonical variational transition state theory (CVT) with the B3LYP/6-311++G(df,pd) MEP of each entrance channel as the reference path. The rate coefficients were evaluated at some selected points along the MEP at a given temperature, and the minima of rate coefficients was taken as the approximate CVT rate coefficient of each entrance channel, and the corresponding structure was regarded as the variational transition state. Figure S3 (Supporting information) shows 6


Page 7 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


the calculated TST rate coefficient curves of channels Rw1 and Rw2 along the MEPs at 298 K and 1.0 bar. The corresponding structures of the minima on the TST curve are taken as the approximate variational transition state. The rate coefficient minima

(kRw1, CVT = 3.52 × 10-12 cm3 molecule−1 s−1 for channel Rw1 and kRw2, CVT = 2.44 × 10-12 cm3 molecule−1 s−1 for channel Rw2) appear at the points where the distances between C and N are 2.98 (for Rw1) and 2.88 Å (for Rw2). These points are exactly at the peak of the MEPs at the CCSD(T)/cc-pVTZ // B3LYP/6-311++G(df,pd) level of theory (Figure S2, Supporting information). He was used as bath gas in the RRKM calculations. The collision frequency was estimated using the Lennard–Jones (L-J) parameters of the intermediates with the bath gas He. The L-J parameters for all the C3H3NO intermediates were estimated by comparison with the analogous ONCH2CHO molecule, and assumed to be σ = 4.75 Å and ε = 450 K48. The L-J parameters of He were set to σ = 2.55 Å and ε / kb= 10.2 K35. The collisional energy transfer parameter was described by the exponential down model with the average downward energy transferred per collision as = 200 (T /298) cm−1 .49 Figure 2 exhibits kRw1, kRw2, kRp1 and ktot (ktot = kRw1 + kRw2 + kRp1) calculated along with the experimental data16 at 195, 296, and 473 K, respectively. The calculated results showed that kRw1 and kRw2 are comparable, while kRp1 is neglectable in the measured temperature and pressure range, and kR12 and kR21 are even lower than kRp1 (Figure S4, Supporting information). The ktot are in good agreement with the experimental results. Table S3 (Supporting information) shows the limiting high- and low-pressure rate 7



coefficients calculated at 195 and 296 K, which are in a good agreement with the data reported by DeSain et al. 16 Figure 3 depicts the temperature dependence of total (ktot = kRw1 + kRw2 + kRp1) along with the forward (kRw1, kRw2, and kRw2 ) and reverse (k-Rw1 and k-Rw2) individual rate coefficients of title reaction at pressures of 0.2 Torr and 1.0 bar and over a temperature range of 200 – 800 K. Both k-Rw1 and k-Rw2 show strong positive temperature dependence, while kRw1 and kRw2 show weak negative temperature dependence, and k-Rw1 = kRw1 at about 500 K; k-Rw2 = kRw2 at about 550 K. kRp1 shows negative temperature dependence at 0.2 Torr, but weak positive temperature dependence at 1.0 bar, and kRw3 is neglectable in the temperature range. The ratio of k-R1w to k-R2w is 11.5 at 473 K and 0.2 Torr, agreeing well with the value of 13 estimated by DeSain et al.16 In the calculated temperature range, the predicted rate coefficients are fitted and expressed in the form of combustion kinetic model in Table 2. Figure 4 exhibits the temperature dependence of branching ratios of channels Rw1, Rw2 and Rp1. At 0.2 Torr, Rp1 is a dominant channel and its branching ratio shows slight positive temperature dependence and greater than 0.66. At 1.0 bar, channels Rw1 and Rw2 are more favorable with comparable branch ratios, while channel Rp1 is ignorable. Figure 5 shows the pressure dependence of the individual and total rate coefficients at 500 K. kRw1 and kRw2 show positive pressure dependence, while kRp1 shows slight negative pressure dependence, and kRw3 is neglectable. Figure 6 shows the pressure dependence of the branching ratios at 500 K. The 8


Page 8 of 20

Page 9 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


branching ratio of channels Rw2 is slight higher than that of Rw1 over a pressure range of 1.0 × 10-3 - 10.0 bar, although they are comparable. Channel Rp1 is more important at a pressure lower than 6.0 × 10-3 bar (with a branching ratio of about 100% at 1.0 × 10-4 bar) and less important after pressure greater than 1.0 × 10-2 bar (with a branching ratio of only 1% at about 1.0 bar).

4. Conclusions The reaction of nitric oxide (NO) with propargyl radical (C3H3) has been investigated at the CCSD(T)/cc-pVTZ//B3LYP/6–311++G(df, pd) level of theory over a temperature range of 200 - 800 K and a pressure range of 1.0 × 10-4 – 10.0 bar. The rate coefficients of the system were determined using RRKM – CVT method with Eckart tunneling correction. Eight channels proceeding via the barrierless formation of excited intermediate ONCH2CCH or CH2CCHNO at the first step were explored, and three favorable channels Rw1, Rw2 and Rp1 were confirmed. The rate coefficients of channels Rw1 and Rw2 are comparable and have weak negative temperature dependence and positive pressure dependence. Channel Rp1 is more important at low pressure and high temperature and less important after pressure greater than 1.0 × 10-2 bar (with a branching ratio less than 6% at about 0.1 bar).

Supporting Information Figures of optimized structures of all stationary points, minimum energy paths and CVT rate coefficients of channels Rw1 and Rw2, calculated rate coefficients of 9



channels R12 and R21. Tables of harmonic vibrational frequencies, ZPEs and T1 diagnostic values of all stationary points, reference enthalpies of formation of reactants and products.

Acknowledgements This work is supported by the National Natural Science Foundation of China (No. 51576139 and 51876141) and key laboratory of high efficiency and low emission engine technology (No. 2017CX02015), ministry of industry and information technology, Beijing institute of technology.

References (1) Adamson, J. D.; DeSain, J. D.; Curl, R. F.; Glass, G. P. Reaction of Cyanomethylene with Nitric Oxide and Oxygen at 298 K: HCCN + NO, O2. J. Phys. Chem. A. 1997, 101, 864 870. (2) Morter, C. L.; Domingo, C.; Farhat, S. K.; Cartwright, E.; Glass, G. P.; Curl, R. F. Rotationally Resolved Spectrum of the ν1 CH Stretch of the Propargyl Radical (H2CCCH). Chem. Phys. Lett. 1992, 195, 316-321. (3) Frassoldati, A.; Faravelli, T.; Ranzi, E. Kinetic Modeling of the Interactions between NO and Hydrocarbons at High Temperature. Combust. Flame. 2003, 135, 97-112. (4) Zhang, J.; Liu, J.; Li, Z.; Sun, C. Theoretical Study on the Reaction Mechanism of the Methyl Radical with Nitrogen Oxides. J. Comput. Chem. 2005, 26, 807-817. (5) Westmoreland, P. R.; Dean, A. M.; Howard., J. B; Longwell, J. P. Forming Benzene in Flames by Chemically Activated Isomerization. J. Phys. Chem. 1989, 93, 8171-8180.

10


Page 10 of 20

Page 11 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(6) Kern, R. D.; Chen, H.; Kiefer, J. H.; Mudipalli, P. S. Thermal Decomposition of Propargyl Bromide and the Subsequent Formation of Benzene. Combust. Flame. 1995, 100, 177-184. (7) Miller, J. A.; Melius, C. F. Kinetic and Thermodynamic Issues in the Formation of Aromatic Compounds in Flames of Aliphatic Fuels. Combust. Flame. 1992, 91, 21-39. (8) Zhai, Y.; Feng, B.; Yuan, W.; Ao, C.; Zhang, L. Experimental and Modeling Studies of Small Typical Methyl Esters Pyrolysis: Methyl Butanoate and Methyl Crotonate. Combust. Flame.

2018, 191, 160-174.

(9) Zhai, Y.; Ao, C.; Feng, B.; Meng, Q.; Zhang, Y.; Mei, B.; Yang, J.; Liu, F.; Zhang, L. Experimental and Kinetic Modeling Investigation On Methyl Decanoate Pyrolysis at Low and Atmospheric Pressures. Fuel. 2018, 232, 333-340. (10) Tranter, R. S.; Yang, X.; Kiefer, J. H. Dissociation of C3H3I and Rates for C3H3 Combination at High Temperatures. Proc. Combust. Inst. 2011, 33, 259-265. (11) Lee, H.; Nam, M.; Choia, J. Ab Initio Investigations of the Radical-Radical Reaction of O (3P) + C3H3. J. Chem. Phys. 2006, 124, 044311. (12) David, K. H.; Stephen, J. K.; James, A. M.; A theoretical analysis of the reaction between propargyl and molecular oxygen. Faraday. Discuss. 2001, 119, 79-100. (13) Dong, F.; Wang, S.; Kong, F. Reaction of Propargyl with Oxygen. J. Phys. Chem. A. 2003, 107, 9374-9379. (14) Crider, P. E.; Castiglioni, L.; Kautzman, K. E.; Neumark, D. M. Photodissociation of the Propargyl and Propynyl (C3D3) Radicals at 248 and 193 Nm. J. Chem. Phys. 2009, 130, 044310. (15) Geppert, W. D.; Eskola, A. J.; Timonen, R. S.; Halonen, L. Kinetics of the Reactions of Vinyl (C2H3) and Propargyl (C3H3) Radicals with NO2 in the Temperature 11



Range 220−340 K. J. Phys. Chem. A. 2004, 108, 4232-4238. (16) DeSain, J. D.; Hung, P. Y.; Thompson, R. I.; Glass, G. P.; Scuseria, G.; Curl, R. F. Kinetics of the Reaction of Propargyl Radical with Nitric Oxide. J. Phys. Chem. A. 2000, 104, 3356-3363. (17) Küpper, J.; Merritt, J. M.; Miller, R. E. Free Radicals in Superfluid Liquid Helium Nanodroplets: A Pyrolysis Source for the Production of Propargyl Radical. J. Chem. Phys. 2002, 117, 647 - 652. (18) Vereecken, L.; Pierloot, K.; Peeters, J. B3LYP-DFT Characterization of the Potential Energy Surface of the CH (X2Ⅱ) + C2H2 Reaction. J. Chem. Phys. 1998, 108, 1068-1080. (19) Le, T. N.; Mebel, A. M.; Kaiser, R. I. Ab Initio Study of C4H3 Potential Energy Surface and Reaction of Ground-State Carbon Atom with Propargyl Radical. J. Comput. Chem. 2001, 13, 1522–1535. (20) Fahr, A.; Nayak, A. Kinetics and Products of Propargyl (C3H3) Self-Reactions and Propargyl-Methyl Cross- Combination Reactions. Int. J. Chem. Kinet. 2000, 32, 118-124. (21) Miller, J. A.; Klippenstein, S. J.; Georgievskii, Y.; Harding, L. B.; Allen, W. D.; Simmonett, A. C.; Reactions between Resonance-Stabilized Radicals: Propargyl + Allyl. J. Phys. Chem. A. 2010, 114, 4881-4890. (22) Matsugi, A.; Miyoshi, A. Computational Study on the Recombination Reaction between Benzyl and Propargyl Radicals. Int. J. Chem. Kinet. 2012, 44, 206 - 218. (23) Frisch, M. J.; Trucks, G.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A. et al. Gaussian 09, Version 7.0, Gaussian, Inc., Wallingford, CT, 2009. 12


Page 12 of 20

Page 13 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(24) Becke, A. D. Density ‐Functional Thermochemistry. I. The Effect of the Exchange ‐Only Gradient Correction. J. Chem. Phys. 1992, 96, 2155-2160. (25) Becke, A. D. Density ‐ Functional Thermochemistry. II. The Effect of the Perdew–Wang Generalized‐Gradient Correlation Correction. J. Chem. Phys. 1992, 97, 9173-9177. (26) Becke, A. D. Density ‐ Functional Thermochemistry. III. The Role of Exact Exchange. J. Chem. Phys. 1993, 98, 5648-5652. (27) Lee, C; Yang, W; Parr, R. G. Development of the Colic-Salvetti Correlation-Energy into a Functional of the Electron Density. Phys. Rev. B. 1988, 37, 785-789. (28) Zhao, Y.; Truhlar, D. G. The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-class Functionals and 12 Other Functionals. Theor. Chem. Acc. 2008, 120, 215-241. (29) Zhao, Y.; Truhlar, D. G. Density Functionals with Broad Applicability in Chemistry. Accounts. Chem. Res. 2008, 41, 157-167. (30) NIST Computational Chemistry Comparison and Benchmark Database, Release 19. http://cccbdb.nist.gov/ (April 2018). (31) Gonzalez, C.; Schlegel, H. B. An Improved Algorithm for Reaction Path Following. J. Chem. Phys. 1989, 90, 2154-2161. (32) Gonzalez, C.; Schlegel, H. B. Reaction Path Following in Mass-Weighted Internal Coordinates. J. Chem. Phys. 1990, 94, 5523-5527. (33) Purvis, G. D.; Bartlett, R. J. A Full Coupled-Cluster Singles and Doubles Model: The Inclusion of Disconnected Triples. J. Chem. Phys. 1982, 76, 1910-1918. 13



Page 14 of 20

(34) Curtiss, L. A.; Redfern, P. C.; Raghavachari, K. Gaussian-4 Theory. J. Chem. Phys. 2007, 126, 084108. (35) Robertson, S. H.; Glowacki, D. R.; Liang, C. H.; Morley, C. M.; Pilling Michael, J. MESMER, An Object-oriented Ctt Program for Carrying Out ME Calculations and Eigenvalue-eigenvector

Analysis

on

Arbitrary

Multiple

Well

Systems.

http://sourceforge.net/projects/mesmer/ (2018). (36) Truhlar, D. G.; Garrett, B. C.; Klippenstein, S. J. Current Status of Transition-State Theory. J. Phys. Chem. A. 1996, 100, 12771-12800. (37) Hase, W. L. Some Recent Advances and Remaining Questions Regarding Unimolecular Rate Theory. Accounts. Chem. Res. 1998, 31, 659-665. (38) Garrett, B. C. Perspective on "the Transition State Method". Theor. Chem. Acc. 2000, 103, 200-204. (39) Holbrook, K. A.; Pilling, M. J.; Robertson, S. H. Unimolecular Reactions; J. Wiley: Chichester, UK, 1996. (40) Li, X.; Cao, H.; Han, D.; Zhang, S.; He, M. The Mechanism and Kinetic Studies for Cl-initiated Oxidation of Allyl Acetate in Troposphere. Comput. Theor. Chem. 2016, 1087, 48-56. (41) Zhao, Z.; Song, J.; Su, B.; Wang, X.; Li, Z. Mechanistic Study of the Reactions of Methyl Peroxy Radical with Methanol or Hydroxyl Methyl Radical. J. Phys. Chem. A. 2018, 122, 5078-5088. (42) Eskola, A. J.; Carr, S. A.; Shannon, R. J.; Wang, B.; Blitz, M. A.; Pilling, M. J.; Seakins, P. W.; Robertson, S. H. Analysis of the Kinetics and Yields of OH Radical Production from the 14


Page 15 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


CH3OCH2 + O2 Reaction in the Temperature Range 195–650 K: An Experimental and Computational Study. J. Phys. Chem. A. 2014, 118, 6773-6788. (43) Eckart, C. The Penetration of a Potential Barrier by Electrons. Phys. Rev. 1930, 35, 1303-1309. (44) Wheeler, S. E.; Robertson, K. A.; Allen, W. D.; Schaefer, H. F. Thermochemistry of Key Soot Formation Intermediates: C3H3 Isomers. J. Chem. Phys. 2007, 111, 3819-3830. (45) Sherrill, C. D. Complete Basis Set Extrapolations for Low-Lying Triplet Electronic States of Acetylene and Vinylidene. J. Chem. Phys. 2000, 4, 1447-1454. (46) Schuurman, M. S.; Muir, S. R.; Allen, W. D.; Schaefer, R. H. F. Toward Subchemical Accuracy in Computational Thermochemistry: Focal Point Analysis of the Heat of Formation of NCO and

H, N, C, O] Isomers. J. Chem. Phys. 2004, 120, 11586.

(47) Lee, T. J.; Taylor, P. R. A Diagnostic for Determining the Quality of Single-Reference Electron Correlation Methods. Int. J. Quantum. Chem. 1989, 199-207. (48) Delbos, E.; Devolder, P.; ElMaimouni, L.; Fittschen, C.; Brudnik, K.; Jodkowski, J. T.; Ratajczak, E. Pressure and Temperature Dependence of the Rate Constants for the Association Reactions of Vinoxy and 1-Methylvinoxy Radicals with Nitric Oxide. Phys. Chem. Chem. Phys. 2002, 4, 2941-2949. (49) Striebel, F.; Jusinski, L. E.; Fahr, A.; Halpern, J. B.; Klippenstein, S. J.; Taatjes, C. A. Kinetics of the Reaction of Vinyl Radicals with NO: Ab Initio Theory, Master Equation Predictions, and Laser Absorption Measurements. Phys. Chem. Chem. Phys. 2004, 6, 2216-2223.

15



Page 16 of 20

Table Pages

Table 1. The relative energies of the species at CCSD(T)/aug-cc-pVTZ, CCSD(T)/cc-pVTZ and G4 levels of theory for C3H3 + NO system. Species

ΔE(0 K) (kcal/mol) CCSD(T)/

CCSD(T) )/

Aug-cc-pVTZ

cc-pVTZ

ΔH(298 K) (kcal/mol) G4

CCSD(T)/

CCSD(T) )/

Aug-cc-pVTZ

cc-pVTZ

G4

Expta

G2b

C3H3 + NO

0.0

0.0

0.0

0.0

0.0

0.0

IM1

-25.2

-23.8

-25.0

-26.4

-24.8

-26.0

-28.1

IM2

-29.8

-28.3

-29.7

-31.2

-29.6

-30.8

-33.1

IM3

-42.2

-43.8

-41.6

-44.1

-44.2

-43.6

IM4

-29.8

-27.1

-28.5

-31.3

-28.4

-32.0

IM5

-25.2

-24.0

-25.1

-26.4

-25.0

-26.4

IM6

-98.3

-97.3

-97.6

-99.7

-98.6

-99.1

IM7

-47.8

-46.6

-47.9

-47.8

-47.7

-50.0

IM8

-38.7

-38.6

-38.4

-38.7

-40.0

-39.9

TS2-3

-2.8

-0.7

-2.4

-4.6

-2.5

-4.3

TS3-P1

-26.9

-25.6

-27.1

-28.7

-27.4

-29.0

TS1-2

3.3

4.6

4.1

1.9

3.2

2.6

TS2-5

25.2

26.5

25.3

24.0

25.3

25.3

TS5-6

6.7

10.3

9.2

5.6

9.3

5.3

TS6-P2

12.8

14.6

13.6

11.8

13.6

12.9

TS2-7

27.0

29.1

27.8

25.7

27.8

25.7

TS7-P3

22.6

24.1

22.7

21.2

22.7

22.1

TS1-4

20.6

23.4

21.9

19.1

22.0

19.2

TS4-8

13.0

15.6

14.4

11.7

14.4

11.9

TS8-P4

10.8

12.5

11.4

9.6

11.4

9.0

P1: HCN + H2CCO

-84.9

-86.0

-85.4

-84.9

-86.3

-85.7

-85.9 (± 0.02)

P2: H2CC + HOCN

-10.2

-10.3

-10.5

-10.1

-10.1

-10.4

-10.2 (± 0.2)

P3: HCCH + HONC

3.9

4.8

3.8

4.3

5.1

4.1

4.7 (± 0.02)

P4: HCCH + HCNO

-10.7

-10.5

-11.6

-10.4

-10.2

-11.2

-10.7(± 0.02)

a Enthalpies b

0.0

of reaction calculated from (Δf H0298) values of the species given in Table S3.

Ref. 16.

All values are relative to the separated reactants.

16


Page 17 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Table 2. Extended Arrhenius parameters a for the rate coefficients of the dominant channels of C3H3 + NO reaction in the temperature range of 200 – 800 K. Rate coefficient 𝑘𝑅𝑤1 𝑘 ―𝑅𝑤1 𝑘𝑅𝑤2 𝑘 ―𝑅𝑤2

A 0.2 bar

n 1.0 bar

6

19

1.28 × 10 4.13 × 10

E (cal mol-1)

0.2 bar

1.0 bar

0.2 bar

1.0 bar

4.26 × 10

7.28

-5.99

5949

11333

-

-8.36

-

109374

-

5

4

7.97 × 10

6.71

-5.68

6104

11466

18

-

8.08

-

118078

-

1.05

-1.63

3969

8176

-0.95

-5.32

5168

10138

3.96 × 10 7.07 × 10

―11

𝑘𝑅𝑝1

4.88 × 10

𝑘𝑡𝑜𝑡

2.03 × 10 ―11

4

9.20 × 10

―9

1.12 × 104

a

Rate coefficients expressed in the extended Arrhenius expression k (T) = A Tn exp (-E/RT) in units of cm3 molecule-1 s-1 (R = 8.314 J molecule-1 K-1 and T in unit of K).

17



Page 18 of 20

Figure Pages

(a) 0

△ E (kcal/mol) C3H3 + NO

(4.6) TS1-2

(0.0)

(-0.7) TS2-3

IM1 (-23.8)

-20

O N H

N C

C

C

H

H

H

-40

TS3-P1 (-25.6)

IM2 (-28.3) C

C

O

C

H

IM3 (-43.8)

H

O

N

H C

C

-60

H

C H

-80

P1: HCN + H2CCO (-86.0)

40

(b)

TS2-7 (29.1)

TS2-5 (26.5)

TS1-4 (23.4)

TS7-P3 (24.1)

20 (15.6) TS4-8

0

TS8-P4 (12.5)

TS5-6 (10.3)

P3 (4.8)

(14.6) TS6-P2

O N

-20

H

C H

-40

C

(-23.8) IM1 H

P4 (-10.5)

IM5 (-24.0)

IM4 (-27.1)

IM2 (-28.3)

H

C

IM8 (-28.3)

H N C

C

O

C

C

H

C

N

C

H

IM7 (-46.6)

O

H

H C

H

H

-60

H

N C

-80

P2: HCCH + HONC

C

C

H

C

C

C

N

C

O

O

P2 (-10.3)

O

H

N

H

H

C

H

H

O

H

P3: H2CC + HOCN

C

H

IM6 (-97.3)

P4: HCCH + HCNO

-100

C

C N

H

Figure 1. The potential energy surface of the favorable (a) and unfavorable (b) reaction channels for the C3H3 + NO system at the CCSD(T)/cc-pVTZ//B3LYP/6-311++G(df, pd) level of theory. 18


Page 19 of 20

1.6

1.0

195 K

(b)

1.4

Rate coefficient × 1011 (cm3s-1)


(a)

1.2 1.0 0.8 0.6 0.4 0.2 0.0 0

1x1018

Density (molecules/cm


(c)

3

296 K 0.8

0.6

0.4

0.2

0.0 0

2x1018

1x1018

2x1018

3x1018

Density (molecules/cm3)

)

0.35

473 K

0.30 0.25 0.20 0.15 0.10 0.05 0.00 0

1x1018

2x1018

Density (molecules/cm3)

3x1018

Figure 2. Comparison of the calculated rate coefficients with the reference data16 at 195 (a), 296 (b), 473 (c) K. (red line, kRw1; blue line, kRw2; green line, kRp1; black line, ktot = kRw1+kRw2+kRp1; black square, reference data).

10-11

10-10 (b)

0.2 Torr

(a)

k/cm3molecule-1s-1

10-15 10-17 10-19 10-21

1.0 bar

10-12

10-13

k/cm3molecule-1s-1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1

2

3

1000/T(K

-1

4

5

10-14 10-16 10-18 10-20

1

2

)

3

1000/T(K-1)

4

5

Figure 3. Temperature dependence of the rate coefficients at 0.2 Torr (a) and 1.0 bar (b). (red solid line, kRw1; red dash line, k-Rw1; blue solid line, kRw2; blue dash line, k-Rw2; gray solid line, kRw3; green solid line, kRp1; black solid line, ktot; violet solid line, calculated high pressure limit; orange solid line, high pressure limit in reference16).

19



1.0 (a)

0.2 Torr

(b)

Branching Ratio

Branching Ratio

0.6

0.4

0.2

0.0

0.6

1.0 bar

0.5

0.8

0.4 0.3 0.2 0.1 0.0

1

2

3

1000/T(K

-1

4

5

1

2

)

3

1000/T(K-1)

4

5

Figure 4. Temperature dependence of the branching ratios at 0.2 Torr (a) and 1.0 bar (b). (red line, for channel Rw1; blue line, for channel Rw2; green line, for channel Rp1).

10-11

500 K

10-12

k/cm3molecule-1s-1

10-13 10-14 10-15 10-19 10-20 10-21 10-4

10-3

10-2

P/bar

10-1

100

101

Figure 5. Pressure dependence of the rate coefficients at 500 K. (red line, kRw1; blue line, kRw2; gray line, kRw3; green line, kRp1; black line, ktot).

1.0

500 K

0.8

Branching Ratio

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 20

0.6

0.4

0.2

0.0 10-4

10-3

10-2

10-1

P/bar

100

101

Figure 6. Pressure dependence of the branching ratios at 500 K. (red line, for channel Rw1; blue line, for channel Rw2; green line, for channel Rp1). 20


Theoretical Study on the Reaction of Nitric Oxide with Propargyl

Recommend Documents