从能量和信息理论视角理解单取代烷烃的异构化

doi:10.3866/PKU.WHXB201708302

Abstract

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 C_nH_2n+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 E_e and the Fisher information or Shannon entropy.

Key words: Molecular stability, Steric hindrance, Density functional theory, Energy component

MSC2000:

O641

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

References

1	Olah G. A. ; Molnur A. Hydrocarbon Chemistry New York: Wiley, 1995.
2	Miao J. ; Hua S. ; Li S. Chem. Phys. Lett. 2012, 541, 7.
3	Wodrich M. D. ; Wannere C. S. ; Mo Y. ; Jarowski P. D. ; Houk K. N. ; Schleyer P. V. R. Chem. Eur. J. 2007, 13 (27), 7731.
4	Allen T. L. J.Chem. Phys. 1959, 31, 1039.
5	Gronert S. Chem. Eur. J. 2009, 15 (21), 5372.
6	Pitzer K. S. ; Catalano E. J.Am. Chem. Soc. 1956, 78, 4844.
7	Ma J. ; Inagaki S. J.Am. Chem. Soc. 2001, 123, 1193.
8	Ito K. J.Am. Chem. Soc. 1953, 75, 2430.
9	Badenhoop J. K. ; Weinhold F. J. Chem. Phys. 1997, 107 (14), 5406.
10	Kemnitz C. R. ; Mackey J. L. ; Loewen M. J. ; Hargrove J. L. ; Lewis J. L. ; Hawkins W. E. ; Nielsen A. F. Chem. Eur. J. 2010, 16 (23), 6942.
11	Weizs?cker C. F. V. Z.Phys. 1935, 96, 431.
12	Liu S. B. J.Chem. Phys. 2007, 126, 244103.
13	Weisskopf V. F. Science 1975, 187, 605.
14	Parr R. G. ; Yang W. Density Functional Theory of Atoms and Molecules Oxford: Oxford University Press, 1989.
15	Chakraborty D. ; Kar S. ; Chattaraj P. K. Phys. Chem. Chem. Phys. 2015, 17, 31516.
16	Liu S. B. ; Govind N. J. Phys. Chem. A 2008, 112 (29), 6690.
17	Liu S. B. ; Govind N ; Pedersen L.G. J. Chem. Phys. 2008, 129 (9), 094104.
18	U?ur ?. ; Vleeschouwer F. D. ; Tüzün N. ; Aviyente V. ; Geerlings P. ; Liu S. B. ; Ayers P. W. ; DeProft F. J. Phys. Chem. A 2009, 113 (30), 8704.
19	Torrent-Sucarrat M. ; Liu S. B. ; DeProft F. J. Phys. Chem. A 2009, 113 (15), 3698.
20	Liu S. B. ; Hu H. ; Pedersen L. G. J.Phys. Chem. A 2010, 114, 5913.
21	Tsirelson V. G. ; Stash A. I. ; Liu S. B. J. Chem. Phys. 2010, 133 (11), 114110.
22	Ess D. H. ; Liu S. B. ; DeProft F. J.Phys. Chem. A 2010, 114, 12952.
23	Zhao D. B. ; Rong C. Y. ; Jenkins S. ; Kirk R. S. ; Yin D. L. ; Liu S. B. Acta Phys. -Chim. Sin. 2013, 29 (1), 43.
23	赵东波; 荣春英; 苏曼; 苏文; 尹笃林; 刘述斌. 物理化学学报, 2013, 29 (1), 43.
24	Wang Y. J. ; Zhao D. B. ; Rong C. Y. ; Liu S. B. Acta Phys. -Chim. Sin. 2013, 29 (10), 2173.
24	王友娟; 赵东波; 荣春英; 刘述斌. 物理化学学报, 2013, 29 (10), 2173.
25	Zhong A. G. ; Chen D. ; Li R. R. Chem. Phys. Lett. 2015, 633, 265.
26	Deb B.M ; Chattaraj P. K. Phys. Rev. A 1989, 39, 1696.
27	Shannon C. E. Bell Syst. Tech. J. 1948, 27, 379.
28	Fisher R. A. Proc. Camb. Philos. Soc. 1925, 22, 700.
29	Bader R. F. W. Atoms in Molecules: A Quantum Theor Oxford: Oxford University Press, 1990.
30	Zhao Y. ; Truhlar D. G. Theor. Chem. Acc. 2008, 120, 215.
31	Valiev M. ; Bylaska E. J. ; Govind N. ; Kowalski K. ; Straatsma T. P. ; van Dam H. J. J. ; Wang D. ; Nieplocha J. ; Apra E. ; Windus T. L. ; et al Comput.Phys. Commun. 2010, 181, 1477.
32	Becke A. D. J.Chem. Phys. 1993, 98, 1372.
33	Lee C. ; Yang W. ; Parr R. G. Phys. Rev. B 1988, 37, 785.
34	Lu T. ; Chen F. J. Comput. Chem. 2012, 33 (5), 580.
35	Lu, T. Multiwfn, Version 3. 3; A Multifunctional Wavefunction Analyzer, 2016, http://multiwfn.codeplex.com (accessed Sep 18, 2016).
36	Grimme S. ; Ehrlich S. ; Goerigk L. J.Comput. Chem. 2011, 32, 1456.
37	Becke A. D. ; Johnson E. R. J.Chem. Phys. 2005, 122, 154104.
38	He?elmann A. J. Chem. Phys. 2009, 130 (8), 084104.
39	Liu S. B. J.Chem. Phys. 2007, 126, 191107.
40	Rong C. Y. ; Lu T. ; Liu S. B. J. Chem. Phys. 2014, 140 (2), 024109.

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Understanding the Isomerization of Monosubstituted Alkanes from Energetic and Information-Theoretic Perspectives

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