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Now showing 1 - 9 of 9

Anharmonic effect of the unimolecular dissociation of Glycerol to Glycidol
(2018-09-01)
Li, Qian
;
Yao, Li
;
Lin, S. H.
;
應用化學系
;
Department of Applied Chemistry
The unimolecular dissociation rate constants of the dehydration of Glycerol to Glycidol were calculated at the MP2/6-311G(d,p) level using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The anharmonic effect of the reactions was examined by comparing the rate constants at temperatures (700-3000 K) of the canonical case and total energies (25654-53089 cm(-1)) of the microcanonical system. The calculations showed that high temperatures are required for the reaction to proceed. As the temperatures and total energies increased, the rate of reactions increased. However, the growth rate of the unimolecular dissociation rate constants was high and slower both in the canonical and microcanonical systems. Comparative analysis showed that the anharmonic effect was most significant for the reaction C -> TSC -> IV + H2O and least significant for the reaction B -> TSB1 -> I + H2O. The anharmonic effect became more significant as the temperatures and total energies increased. Compared with the microcanonical situation, the anharmonic effect of the canonical system was more pronounced.
Computational Study on the Reactions of H2O2 on TiO2 Anatase (101) and Rutile (110) Surfaces
(2011-04-30)
Huang, Wen-Fei
;
Raghunath, P.
;
Lin, M. C.
;
應用化學系分子科學碩博班
;
Institute of Molecular science
This study investigates the adsorption and reactions of H2O2 on TiO2 anatase (101) and rutile (110) surfaces by first-principles calculations based on the density functional theory in conjunction with the projected augmented wave approach, using PW91, PBE, and revPBE functionals. Adsorption mechanisms of H2O2 and its fragments on both surfaces are analyzed. It is found that H2O2, H2O, and HO preferentially adsorb at the Ti-5c site, meanwhile HOO, O, and H preferentially adsorb at the (O-2c)(Ti-5c), (Ti-5c)(2), and O-2c sites, respectively. Potential energy profiles of the adsorption processes on both surfaces have been constructed using the nudged elastic band method. The two restructured surfaces, the 1/3 ML oxygen covered TiO2 and the hydroxylated TiO2, are produced with the H2O2 dehydration and deoxidation, respectively. The formation of main products, H2O(g) and the 1/3 ML oxygen covered TiO2 surface, is exothermic by 2.8 and 5.0 kcal/mol, requiring energy barriers of 0.8 and 1.1 kcal/mol on the rutile (110) and anatase (101) surface, respectively. The rate constants for the H2O2 dehydration processes have been predicted to be 6.65 x 10(-27) T-4.38 exp(-0.14 kcal mol(-1)/RT) and 3.18 x 10(-23) T-5.60 exp(-2.92 kcal mol(-1)/RT) respectively, in units of cm(3) molecule(-1) s(-1). (C) 2010 Wiley Periodicals, Inc. J Comput Chem 32: 1065-1081, 2011
Calculation of anharmonic effect on the dissociation of ethylene glycol
(2017-12-01)
Li, Qian
;
Yao, Li
;
Lin, S. H.
;
應用化學系
;
Department of Applied Chemistry
The unimolecular dissociation rate constants of ethylene glycol were examined using the MP2/6-311++G(d, p) method based on the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The effect of anharmonicity on the dissociation rate constants was evaluated at 500-4000 K temperatures of the canonical system and 25,182-50,235 cm(-1) total energies of the microcanonical system. The comparison of the results showed that the H2O elimination reaction played a critical role in the decomposition processes of ethylene glycol. The results of the rate constant calculations indicated that the H2O elimination reaction dominated at low temperatures, whereas the direct C-C bond dissociation reaction (CH2OHCH2OH -> CH2OH+CH2OH) dominated at high temperatures. For channel 1, CH2OH+CH2OH, the anharmonic effect of the canonical system was not observed, while it became more obvious with the increasing total energies in the microcanonical system. For channels 2-5, CH3CHO+H2O, CH2CHOH+H2O, CH3OH+CHOH, and CH2OHCHO+H-2, the anharmonic effect of canonical and microcanonical systems became more obvious with increasing temperatures and total energies. The comparison showed that, for channels 1 and 4, C-C bond dissociation and the anharmonic effect of the microcanonical system were more evident, whereas the anharmonic effect of the canonical system was more predominant for channels 2 (CH3CHO+H2O), 3 (CH2CHOH+H2O), and 5 (CH2OHCHO+H-2).
Calculation of anharmonic effects in the unimolecular dissociation of M2+ (H2O)(2) (M = Be, Mg, and Ca)
(2015-11-17)
Li, Qian
;
Yao, Li
;
Xia, Wenwen
;
Lin, S. H.
;
應用化學系
The anharmonic and harmonic rate constants of the unimolecular dissociation of M2+(H2O)(2) (M = Be, Mg, and Ca) were calculated using the Rice-Ramsperger-Kassel-Marcus theory. The anharmonic effects of the reactions were investigated. The results show that the energy barrier of the dissociation of Be2+(H2O)(2) is 68.47 kcal/mol, and the anharmonic (T-4000K = 4.28x10(8) s(-1)) and harmonic (T-4000K = 4.22x10(8) s(-1)) rate constants were close in value in both the canonical and microcanonical systems. The energy barriers of the two steps for the dissociation, Mg2+(H2O)(2) MgOH++H3O+, were 37.41 and 11.39 kcal/mol, and those for the dissociation, Ca2+(H2O)(2) CaOH++H3O+, were 21.15 and 26.42 kcal/mol. The anharmonic effect of the two reactions is significant and cannot be neglected in both the canonical and microcanonical systems. The comparison also shows that the rate constants of the dissociation of Ca2+(H2O)(2) have the maximum values, while those of Be2+(H2O)(2) have the minimum values in the three reactions; however, the anharmonic effect also shows the similar trend in the comparison.
Anharmonic effect of the unimolecular dissociation of CH3COOH
(2014-11-02)
Zhang, Liwei
;
Yao, Li
;
Li, Qian
;
Wang, Guiqiu
;
Lin, S. H.
Anharmonic and harmonic rate constants of the reactions have been calculated with the Rice-Ramsperger-Kassel-Marcus theory, and the anharmonic results are higher than the harmonic ones. The anharmonic effect and isotopic effect on the decomposition reactions have also been examined. The anharmonic effect in all the four reactions is obvious, especially at the high temperatures or energies. Relatively, the anharmonic effect on the reaction trans-acetic acid -> TS2 radical is the least obvious among the four reactions. In the microcanonical system, the difference of the rate constants between the deuterated results and the non-deuterated results is not negligible; in other words, the isotopic effect is obvious in all the four reactions. Among these reactions, three of the deuterated results (d, d3 and d4) have a big difference.
Calculation of anharmonic effects for the unimolecular dissociation of CH3OOH and its deuterated species CD3OOD using the Rice-Ramsperger-Kassel-Marcus theory
(2015-06-01)
Li, Qian
;
Yao, Li
;
Lin, S. H.
;
應用化學系
;
Department of Applied Chemistry
Anharmonic and harmonic rate constants for the unimolecular dissociation of CH3OOH and CD3OOD were calculated using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory at the MP2/6-311++G(3df,3pd) level of theory. The anharmonic effect of the reactions was investigated. Comparison of results for the decompositions of CH3OOH and CD3OOD shows that the direct bond dissociation channel, CH3 (D-3) O + OH (D), is the most dominant reaction. The anharmonic effect plays an important role in the unimolecular dissociation of both CH3OOH and CD3OOD. For channels CH3 (D-3) O + OH (D) and CH3 (D-3) + H (D) O-2, the anharmonic effect of the unimolecular dissociation of CD3OOD is more pronounced than that of the unimolecular dissociation of CH3OOH. For channel H-2 (D-2) CO + H-2 (D-2) O, the anharmonic effect of the unimolecular dissociation of CH3OOH is more pronounced than that of the unimolecular dissociation of CD3OOD. The isotope effect is more distinct in the anharmonic oscillator model.
The anharmonic effect study of coupled Morse oscillators for the unimolecular reaction
(2008-12-01)
Yao Li
;
Lin Sheng-Hsien
;
應用化學系
;
應用化學系分子科學碩博班
;
Department of Applied Chemistry
The importance of anharmonic effect in dissociation of molecular systems especially clusters has been noted. In this paper, we shall study the effect of coupled anharmonic oscillator of the standard bilinear form (SBF) Morse oscillator (MO) potential on unimolecular reaction. We shall use the systematic theoretical approach, YL method, proposed by Yao and Lin (YAO L, et. al. J Phys Chem A, 2007, 111( 29): 6722-6729), which can evaluate anharmonic effects on the rate constants based on the transition state theory. In treating the anharmonic effect with the Morse oscillator potential on unimolecular reactions under collision-free conditions by using the RRKM (Rice-Ramsperger-Kassel-Marcus) theory, the inverse Laplace transformation of the partition functions was used to obtain the total amount of state and density of state by using the first-order and the second-order approximations of the saddle-point method. To demonstrate the anharmonic effect of the SBF Morse model, we choose some model systems and a real reaction as examples.
Ab Initio Chemical Kinetics for Reactions of H Atoms with SiHx (x=1-3) Radicals and Related Unimolecular Decomposition Processes
(2013-06-15)
Raghunath, Putikam
;
Lee, Yun-Min
;
Wu, Shang-Ying
;
Wu, Jong-Shinn
;
Lin, Ming-Chang
Hydrogen atoms and SiHx (x = 1-3) radicals coexist during the chemical vapor deposition (CVD) of hydrogenated amorphous silicon (a-Si: H) thin films for Si-solar cell fabrication, a technology necessitated recently by the need for energy and material conservation. The kinetics and mechanisms for H-atom reactions with SiHx radicals and the thermal decomposition of their intermediates have been investigated by using a high high-level ab initio molecular-orbital CCSD (Coupled Cluster with Single and Double)(T)/CBS (complete basis set extrapolation) method. These reactions occurring primarily by association producing excited intermediates, (SiH2)-Si-1, (SiH2)-Si-3, SiH3, and SiH4, with no intrinsic barriers were computed to have 75.6, 55.0, 68.5, and 90.2 kcal/mol association energies for x = 1-3, respectively, based on the computed heats of formation of these radicals. The excited intermediates can further fragment by H-2 elimination with 62.5, 44.3, 47.5, and 56.7 kcal/mol barriers giving Si-1, Si-3, SiH, and (SiH2)-Si-1 from the above respective intermediates. The predicted heats of reaction and enthalpies of formation of the radicals at 0 K, including the latter evaluated by the isodesmic reactions, SiHx + CH4 SiH4 + CHx, are in good agreement with available experimental data within reported errors. Furthermore, the rate constants for the forward and unimolecular reactions have been predicted with tunneling corrections using transition state theory (for direct abstraction) and variational Rice-Ramsperger-Kassel-Marcus theory (for association/decomposition) by solving the master equation covering the P, T-conditions commonly employed used in industrial CVD processes. The predicted results compare well experimental and/or computational data available in the literature. (C) 2013 Wiley Periodicals, Inc.
THEORETICAL STUDIES OF ANHARMONIC EFFECT IN THE RICE RAMSPERGER KASSEL MARCUS THEORY
(2008-12-20)
Yao, L.
;
Liu, Y. L.
;
Lin, S. H.
;
應用化學系
;
Department of Applied Chemistry
The purpose of this paper is to propose a theoretical approach, which can evaluate anharmonic effects on the rate constants within the transition state theory. In treating unimolecular reactions under collision-free conditions by using the RRKM theory, we make use of the inverse Laplace transformation of the partition functions to obtain both the total number of states for the activated complex and density of states for the reactant with the Morse oscillator potential. To demonstrate the applications of our theoretical approach, we choose some model systems and a real reaction as examples.

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