Theoretical Investigation on the Reaction Between HRnCCH and X(X=H2O, NH3) in Gas Phase†

doi:10.7503/cjcu20130863

Abstract

Abstract:

The reaction mechanisms of HRnCCH with H₂O, NH₃ were explored at the CCSD(T)//MP2/aug-cc-pVTZ-pp level of theory. This investigation involved the conversion between HRnCCH and HRnOH, HRnCCH and HRnNH₂, and the water, water dimer, and ammonia gas molecule addition to the C≡C bond in the HRnCCH, respectively. The calculated results show that the HCCH+HRnOH is produced by the reaction of HRnCCH+H₂O with an activated barrier of 54.1 kJ/mol and HCCH+HRnNH₂ is yielded via the reaction of HRnCCH+NH₃ with a estimated barrier of 75.2 kJ/mol. However, the formations of HRnCHC(OH)H, HRnC(OH)CH₂, HRnCHC(NH₂)H and HRnC(NH₂)CH₂ have the respective barrier of 219.6, 220.5, 174.4 and 182.4 kJ/mol. Therefore, the reactivity of HRnCCH is of quite weakness at the environments investigated herein, which indicates that HRnCCH could be existed under these conditions. In addition, the second water molecule introduced into the HRnCCH+H₂O reaction leads to the remarkable reduction for the barrier of the formation of HRnCHC(OH)H to 123.2 kJ/mol, in which the second water molecule plays a strong catalytic role in the reaction of HRnCCH with water.

Key words: HRnCCH, Quantum chemical calculation, Reaction mechanism, Water, Ammonia gas

CLC Number:

O641

TrendMD:

GAO Chenggui, LONG Zhengwen, TAN Xingfeng, LONG Bo, ZHANG Weijun, LONG Chaoyun, QIN Shuijie. Theoretical Investigation on the Reaction Between HRnCCH and X(X=H₂O, NH₃) in Gas Phase^†[J]. Chem. J. Chinese Universities, 2014, 35(2): 344.

Figures/Tables 7

Table 1 Properties of the studied H-bonded complexesa

H-Bond type	E_HB/(kJ·mol^-1)	R(H…X)/nm	R(Y…H)/nm	$ν ˙$ (Y…H)/cm^-1
RC1(H₂O…HRnCCH)	4.6	0.2435	0.1807	1761.99
RC2(H₃N…HRnCCH)	7.5	0.2277	0.1806	1699.26
RC3(HRnCCH…OH₂)	5.1	0.2238	0.1069	3403.46
RC4(HRnCCH…NH₃)	3.7	0.2318	0.1072	3351.37
HCCH…OH₂	1.4^b	0.2186 ^b	0.1067 ^b	3392.80 ^b
HCCH…NH₃	1.7 ^b	0.2259 ^b	0.1071 ^b	3334.88 ^b

Table 1 Properties of the studied H-bonded complexesa

H-Bond type	E_HB/(kJ·mol^-1)	R(H…X)/nm	R(Y…H)/nm	$ν ˙$ (Y…H)/cm^-1
RC1(H₂O…HRnCCH)	4.6	0.2435	0.1807	1761.99
RC2(H₃N…HRnCCH)	7.5	0.2277	0.1806	1699.26
RC3(HRnCCH…OH₂)	5.1	0.2238	0.1069	3403.46
RC4(HRnCCH…NH₃)	3.7	0.2318	0.1072	3351.37
HCCH…OH₂	1.4^b	0.2186 ^b	0.1067 ^b	3392.80 ^b
HCCH…NH₃	1.7 ^b	0.2259 ^b	0.1071 ^b	3334.88 ^b

Fig.1 Optimized geometries of H2O…HRnCCH and H3N…HRnCCH and their corresponding transition states and products at MP2/aug-cc-pVTZ-pp level of theory Bond lengths are in nm.

Fig.2 Potential energy profiles at CCSD(T)//MP2/aug-cc-pVTZ-pp level of theoryThe reactions begin with the forming of hydrogen-bonded reactant complexes: (A) X…HRnCCH(X=H2O or NH3);(B) HRnCCH…OH2; (C) HRnCCH…NH3.

Table 2 Activated energies(ΔE), enthalpies(ΔH), free energies(ΔG) for the HRnCCH+X(X=H2O, NH3) reactions added with zero-point correction included at 298 K

Reaction	ΔH^a /(kJ·mol^-1)	ΔG^a/(kJ·mol^-1)	ΔE^a/(kJ·mol^-1)	ΔE^b/(kJ·mol^-1)	T1^c
HRnCCH+H₂O	0	0	0	0	0.012, 0.010
RC1	-2.9	14.0	-4.9	-4.6	0.012
TS1	42.8	79.5	47.8	54.1	0.012
P1	22.7	29.8	27.0	-2.9	0.013, 0.013
RC3	-5.1	15.6	-75.2	-5.1	0.012
TS3	207.9	248.3	214.3	219.6	0.015
TS3a	214.2	254.2	220.5	220.5	0.016
P3	-72.9	-30.9	-66.1	-89.7	0.013
P3a	-76.0	-35.2	-69.5	-92.5	0.013
HCCH+H₂O			222.2, 241.8, 243.9^d
HRnCCH+NH₃	0	0	0	0	0.012, 0.008
RC2	-5.7	15.9	-7.0	-7.5	0.012
TS2	67.2	102.8	71.6	75.2	0.012
P2	23.5	23.6	25.7	43.1	0.011, 0.013
RC4	-7.3	14.6	-8.1	-3.7	0.012
TS4	165.9	209.6	173.2	174.4	0.014
TS4a	174.4	217.7	181.7	182.4	0.014
P4	-75.5	-31.0	-67.7	-86.6	0.012
P4a	-105.9	-63.4	-99.3	-114.2	0.013
HCCH+NH₃			181.2, 182.0, 190.4, 192.9^d

Fig.3 Optimized geometries of HRnCCH…OH2 and HRnCCH…NH3 and their corresponding transition states and products at the MP2/aug-cc-pVTZ-pp level of theoryBond lengths are in nm.

Fig.4 Optimized geometries of RCH2O(A) and TSH2O(B) at the MP2/aug-cc-pvtz-pp level of theory Bond lengths are in nm.

Table 3 Activated energies(ΔE), enthalpies(ΔH) and free energies(ΔG) for the HRnCCH…H2O+H2O reactions with zero-point correction included at 298 K

Reaction	ΔH^a /(kJ·mol^-1)	ΔG^a/(kJ·mol^-1)	ΔE^a/(kJ·mol^-1)	ΔE^b/(kJ·mol^-1)	T1^c
HRnCCH…H₂O+H₂O	0.0	0.0	0.0	0.0	0.012, 0.010
R $C H 2 O$	-45.1	16.6	-41.8	-55.3	0.012
T $S H 2 O$	110.8	196.4	122.9	123.2	0.016

Table 3 Activated energies(ΔE), enthalpies(ΔH) and free energies(ΔG) for the HRnCCH…H2O+H2O reactions with zero-point correction included at 298 K

Reaction	ΔH^a /(kJ·mol^-1)	ΔG^a/(kJ·mol^-1)	ΔE^a/(kJ·mol^-1)	ΔE^b/(kJ·mol^-1)	T1^c
HRnCCH…H₂O+H₂O	0.0	0.0	0.0	0.0	0.012, 0.010
R $C H 2 O$	-45.1	16.6	-41.8	-55.3	0.012
T $S H 2 O$	110.8	196.4	122.9	123.2	0.016

References 40

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Theoretical Investigation on the Reaction Between HRnCCH and X(X=H₂O, NH₃) in Gas Phase^†

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