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Acta Phys. -Chim. Sin.  2018, Vol. 34 Issue (3): 303-313    DOI: 10.3866/PKU.WHXB201708302
Special Issue: Special issue for Chemical Concepts from Density Functional Theory
    
Understanding the Isomerization of Monosubstituted Alkanes from Energetic and Information-Theoretic Perspectives
Aiguo ZHONG*(),Rongrong LI,Qin HONG,Jie ZHANG,Dan CHEN
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Abstract  

A unified explanation for the relative stability of linear and branched alkanes is still lacking, and research in this direction is ongoing. Unlike the conventional orbital-based description, we have employed the density functional theory (DFT) based on the total energy and its components as well as a newly proposed energy partitioning scheme [Liu, S. B. J. Chem. Phys. 2007, 126, 244103]. Taking monosubstituted hydrocarbons CnH2n+1―R (n = 3, 4, 5, 6; R = OH, OCH3, NH2, NO2, F, Cl, CN, CHO) as examples, we have investigated the molecular origin and nature within the framework of the DFT. Our computational results revealed that no such a single energy component that dictates the transformation of the mono-substituted alkane derivatives. By the binary fit of the electrostatic potential and steric hindrance from the new energy decomposition scheme, we unraveled that isomerization is mainly governed by the electrostatic potential, while the steric effect has a minor influence. Moreover, we established a linear relationship between the Shannon entropy difference and the Fisher information difference, which is accordance with previous findings. Further, there was no linear relationship between Ee and the Fisher information or Shannon entropy.



Key wordsMolecular stability      Steric hindrance      Density functional theory      Energy component     
Received: 19 July 2017      Published: 30 August 2017
O641  
Fund:  the Natural Science Foundation of Zhejiang Province, China(LY15B030001);the Natural Science Foundation of Zhejiang Province, China(LY15B060001);Zhejiang Province Undergraduate Student Innovation Project, China(2017R430014)
Corresponding Authors: Aiguo ZHONG     E-mail: zhongaiguo@tzc.edu.cn
Cite this article:

Aiguo ZHONG,Rongrong LI,Qin HONG,Jie ZHANG,Dan CHEN. Understanding the Isomerization of Monosubstituted Alkanes from Energetic and Information-Theoretic Perspectives. Acta Phys. -Chim. Sin., 2018, 34(3): 303-313.

URL:

http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201708302     OR     http://www.whxb.pku.edu.cn/Y2018/V34/I3/303

 
R M06-2X M06-2X b B3LYP B3LYP_D3BJ B3LYP_XDM B3LYP_DCP HF MP2 CCSD(T)
―OH -15.5 -15.3 -13.5 -14.4 -14.7 -17.3 -11.9 -16.9 -16.3
―OCH3 -10.7 -10.0 -7.0 -8.9 -9.4 -14.6 -4.6 -12.5 -11.7
―NH2 -12.2 -12.1 -9.4 -10.7 -11.0 -15.4 -8.2 -14.5 -13.1
―NO2 -13.5 -13.0 -9.4 -11.0 -11.0 -17.3 -7.9 -15.3 -14.0
―F -18.9 -18.7 -18.4 -18.5 -18.7 -20.1 -16.8 -19.6 -19.4
―Cl -11.3 -11.1 -9.1 -10.4 -10.4 n.a. c -7.4 -13.9 -12.2
―CN -2.3 -2.3 -0.1 -1.4 -1.5 -5.7 -0.1 -5.2 -3.6
―CHO -5.1 -4.9 -1.8 -3.3 -3.3 -9.3 -0.8 -7.0 -5.6
MAE d 0.8 1.0 3.4 2.2 2.0 2.3 4.8 1.1
MSE e 0.8 1.0 3.4 2.2 2.0 -2.3 4.8 -1.1
 
Reaction Ts Es Ex Ec Exc Ee Eq Etot
C3-serials 18.4 -97.8 10.9 -5.9 5.0 -38.9 121.2 -15.5
5.9 -131.7 9.6 -10.0 -0.4 -16.3 137.1 -10.5
11.3 -103.7 11.3 -7.1 4.2 -28.0 119.1 -12.1
23.0 -104.1 4.2 -8.4 -3.8 -32.6 123.3 -13.4
25.5 -106.6 6.7 -4.2 2.5 -46.8 134.6 -18.8
7.9 -89.0 12.1 -6.3 5.4 -25.1 102.8 -11.3
13.0 -160.1 7.5 -10.5 -2.9 -27.2 170.1 -17.6
5.9 -185.2 4.6 -14.2 -9.6 -8.8 181.4 -12.5
C4-serials 10.5 -157.2 7.1 -12.1 -4.6 -20.5 163.0 -14.6
18.8 -143.8 0.4 -13.0 -12.5 -22.6 150.1 -15.9
22.6 -158.8 2.9 -8.4 -5.4 -38.0 176.0 -20.9
3.3 -137.1 9.6 -11.3 -1.7 -15.0 139.2 -13.4
3.8 -50.2 5.0 -8.4 -3.3 -3.8 50.6 -3.3
7.1 -172.6 -0.4 -13.8 -14.6 -2.9 165.1 -10.5
7.9 -150.5 5.0 -10.9 -5.9 -12.5 152.6 -10.5
9.2 -143.8 5.0 -10.9 -5.9 -13.8 147.6 -10.0
8.8 -141.3 5.0 -11.3 -6.3 -11.7 143.8 -9.2
11.3 -159.3 6.3 -14.2 -7.9 -15.9 162.2 -13.0
10.5 -135.9 5.4 -9.6 -4.2 -16.7 142.1 -10.5
4.6 -143.8 7.1 -11.7 -4.6 -9.6 143.4 -9.6
5.4 -135.0 6.7 -11.3 -4.6 -11.7 135.9 -10.9
7.5 -129.2 6.7 -11.3 -5.0 -12.1 132.1 -9.6
40.5 -244.1 17.1 -18.4 -1.3 -76.5 283.8 -36.8
27.6 -307.6 11.7 -27.2 -15.5 -38.9 319.8 -27.2
30.9 -222.0 20.1 -20.5 -0.4 -60.2 252.5 -30.1
35.9 -308.9 7.5 -26.3 -18.8 -48.9 326.0 -32.2
15.0 -149.6 7.5 -10.5 -2.9 -28.8 161.8 -16.7
6.3 -194.8 3.3 -15.9 -12.5 -2.5 188.5 -8.8
5.4 -127.1 7.9 -12.5 -4.2 -7.5 128.3 -6.3
22.6 -304.3 11.3 -23.0 -11.7 -36.4 315.2 -25.5
21.7 -311.0 8.8 -24.2 -15.5 -30.5 317.3 -24.2
33.9 -331.1 15.0 -26.8 -11.3 -57.7 353.6 -35.1
C5-serials 22.6 -339.4 10.9 -28.4 -17.6 -29.7 344.9 -24.2
8.4 -173.9 4.6 -14.2 -9.6 -10.5 173.1 -11.7
7.9 -188.5 3.3 -15.9 -12.5 -4.6 184.3 -8.8
6.7 -126.7 7.9 -12.5 -4.2 -8.8 129.2 -6.3
22.6 -310.6 8.8 -26.3 -17.6 -25.5 316.0 -20.5
21.3 -331.9 6.3 -28.8 -22.6 -18.8 331.1 -20.1
19.6 -397.1 10.0 -35.9 -26.3 -17.6 390.8 -24.2
29.7 -325.2 10.9 -28.0 -17.6 -36.4 337.7 -24.2
12.5 -148.8 7.5 -12.1 -4.6 -21.7 156.8 -14.2
8.4 -190.6 4.2 -16.7 -12.5 -3.8 186.0 -7.9
7.5 -134.6 7.1 -12.5 -5.4 -9.2 136.7 -7.1
18.8 -267.9 15.0 -25.1 -10.0 -27.2 276.7 -18.4
20.1 -304.3 8.8 -26.3 -17.6 -23.4 307.2 -20.9
25.9 -310.2 18.4 -29.3 -10.9 -43.1 324.8 -28.0
23.8 -345.3 13.0 -30.5 -17.6 -29.3 351.5 -23.0
20.9 -135.0 0.4 -13.0 -12.5 -23.8 143.4 -15.9
8.4 -203.1 5.0 -18.8 -13.8 -6.3 197.7 -11.7
5.9 -129.6 7.5 -12.1 -4.6 -7.9 130.8 -6.7
33.0 -309.7 5.4 -28.4 -23.0 -37.2 319.4 -27.6
22.2 -363.2 4.2 -32.6 -28.4 -19.2 357.4 -25.5
32.2 -383.7 5.0 -35.1 -30.1 -32.6 385.8 -30.5
19.2 -347.4 17.1 -34.7 -17.1 -25.1 349.9 -23.0
24.2 -148.8 2.9 -8.4 -5.4 -38.9 167.6 -20.1
8.8 -178.5 4.2 -14.6 -10.5 -7.1 176.8 -8.8
5.4 -126.2 7.5 -12.1 -4.2 -7.1 127.1 -5.9
34.7 -289.3 7.5 -19.2 -12.1 -52.3 311.8 -29.3
32.6 -296.8 4.6 -20.9 -16.3 -44.3 313.5 -28.0
50.6 -336.5 6.7 -22.2 -15.5 -77.3 372.0 -42.2
27.2 -311.0 12.5 -25.9 -13.8 -38.0 324.8 -24.2
5.9 -130.0 9.2 -11.3 -2.1 -16.7 133.8 -13.0
3.3 -188.9 5.4 -17.1 -11.3 -0.4 181.0 -8.4
2.1 -132.5 7.1 -12.1 -5.0 -3.8 129.6 -6.3
9.2 -281.7 16.3 -25.5 -9.6 -20.5 281.3 -20.5
7.5 -285.1 13.0 -25.5 -12.5 -15.0 279.6 -20.5
12.1 -310.6 20.1 -28.4 -8.8 -31.4 313.9 -28.4
13.8 -334.8 15.0 -30.9 -15.5 -22.2 333.6 -23.8
6.7 -44.7 4.6 -8.8 -3.8 -5.9 47.2 -3.3
4.6 -183.9 5.9 -16.7 -10.9 -4.2 177.7 -10.0
6.3 -135.4 6.7 -12.1 -5.4 -7.5 136.3 -6.7
13.8 -198.1 10.5 -22.2 -11.7 -15.9 200.2 -13.8
C6-serials 8.4 -201.9 8.4 -22.6 -14.6 -5.9 195.6 -12.1
21.7 -163.0 12.1 -23.8 -11.7 -21.7 173.1 -12.1
21.7 -321.0 14.6 -30.1 -15.0 -33.0 327.7 -26.3
9.2 -171.4 0.0 -14.2 -14.6 -5.0 165.9 -10.5
5.9 -179.3 5.9 -16.7 -10.9 -3.8 174.7 -8.8
6.3 -137.1 6.7 -12.5 -5.9 -7.5 137.5 -7.1
13.0 -247.5 9.2 -24.2 -14.6 -12.1 245.8 -13.8
13.4 -330.2 2.5 -28.8 -26.3 -2.9 317.3 -15.9
19.6 -334.0 5.9 -31.4 -25.5 -14.2 328.5 -20.1
15.9 -293.9 16.3 -30.9 -14.6 -20.5 294.7 -19.6
15.0 -151.7 7.9 -10.9 -2.9 -29.3 164.3 -16.7
7.9 -191.9 3.8 -16.3 -12.1 -4.6 187.7 -8.8
1.3 -174.3 7.1 -17.1 -9.6 4.2 165.5 -4.2
7.5 -134.2 7.5 -12.5 -5.0 -9.6 136.7 -7.1
12.1 -329.0 8.8 -31.4 -22.6 -1.7 318.5 -12.5
23.4 -299.7 14.2 -25.9 -11.7 -37.2 311.4 -25.1
28.8 -248.3 20.9 -24.2 -3.3 -41.4 273.8 -15.9
22.6 -357.8 10.5 -30.1 -19.6 -26.8 361.2 -23.8
21.7 -353.2 8.4 -29.3 -21.3 -23.8 353.6 -23.4
38.0 -318.5 15.9 -26.8 -10.9 -61.4 345.7 -34.7
15.5 -431.4 7.9 -37.6 -29.7 -7.1 417.2 -21.3
15.9 -295.5 16.7 -30.1 -13.4 -19.2 298.0 -16.7
8.4 -176.0 5.0 -14.6 -9.6 -10.9 174.7 -11.7
9.2 -186.0 3.8 -15.9 -12.1 -5.9 183.1 -8.8
2.5 -173.5 7.1 -17.1 -10.0 2.9 165.9 -4.2
7.5 -133.8 7.5 -12.5 -5.0 -9.6 136.3 -7.1
15.0 -382.9 8.8 -30.9 -22.6 -5.0 375.8 -12.5
18.0 -420.1 11.3 -29.7 -18.0 -20.1 419.7 -20.5
20.9 -294.3 18.0 -28.0 -10.0 -21.3 305.1 -10.9
23.0 -362.4 8.4 -33.4 -25.1 -16.7 360.7 -18.8
20.1 -372.4 5.9 -33.9 -28.4 -10.5 364.5 -18.8
24.7 -382.9 10.5 -36.4 -25.9 -22.2 381.6 -23.4
20.1 -420.1 7.5 -37.6 -29.7 -11.3 410.1 -21.3
17.6 -294.3 16.7 -30.5 -13.4 -20.9 298.5 -16.7
12.5 -150.5 7.5 -12.1 -4.6 -22.2 158.4 -14.2
10.5 -187.3 4.6 -16.7 -12.5 -5.9 185.2 -7.9
3.3 -181.8 6.3 -17.1 -10.9 2.5 174.3 -5.0
7.1 -133.3 7.5 -12.5 -5.0 -8.8 135.4 -7.1
14.6 -334.0 7.9 -32.2 -24.2 -2.9 324.4 -12.5
21.3 -296.4 14.2 -27.6 -13.4 -30.5 304.7 -22.6
27.6 -247.5 20.5 -25.9 -5.4 -35.5 269.6 -13.4
19.2 -326.0 14.2 -32.6 -18.0 -18.0 327.7 -16.7
20.5 -349.9 8.4 -32.2 -23.4 -16.7 346.5 -20.1
30.1 -298.5 18.8 -29.7 -10.9 -46.8 317.7 -27.6
19.2 -436.8 10.5 -40.1 -30.1 -9.2 425.9 -20.1
19.6 -300.1 16.7 -30.9 -14.6 -22.6 305.1 -17.1
20.9 -136.3 0.4 -13.0 -12.5 -24.2 144.6 -15.9
10.5 -199.8 5.0 -19.2 -14.2 -7.9 196.0 -11.7
1.3 -176.4 6.3 -16.7 -10.0 3.8 167.6 -5.0
5.9 -133.8 7.5 -12.5 -5.0 -7.9 134.2 -7.1
15.5 -337.3 8.8 -33.4 -24.7 -6.3 328.5 -15.5
29.3 -301.8 6.7 -28.8 -22.2 -32.6 308.9 -25.5
31.8 -250.4 13.4 -26.3 -13.0 -34.3 268.8 -15.5
32.2 -358.6 4.2 -35.1 -30.9 -27.2 359.9 -25.9
20.1 -398.8 3.8 -36.8 -33.0 -10.9 385.8 -23.8
36.8 -370.8 5.4 -35.5 -30.5</