Orbital responses to methyl sites in CnH2n+2 (n=1–6)

doi:10.1088/1674-1056/21/2/023401

Abstract Orbital responses to methyl sites in C_nH_2n+2 (n=1-6) are studied by B3LYP/TZVP based on the most stable geometries using the B3LYP/aug-cc-pVTZ method. Vertical ionization energies are produced using the SAOP/et-pVQZ model for the complete valence space. The highest occupied molecular orbital (HOMO) investigations indicate the p-electron profiles in methane, ethane, propane, and n-butane. By increasing the number of carbon-carbon bonds in lower momentum regions, the s, p-hybridized orbitals are built and display strong exchange and correlation interactions in lower momentum space (P$\lesssim$0.50 a.u.). Meanwhile, the relative intensities of the isomers in lower momentum space show the strong bonding number dependence of the carbon-carbon bonds, meaning that more electrons have contributed to orbital construction. The study of representative valence orbital momentum distribution further confirms that the structural changes lead to evident electronic rearrangement over the whole valence space. An analysis based on the isomers reveals that the valence orbitals are isomer-dependent and the valence ionization energy experiences an apparent shift in the inner valence space. However, such shifts are greatly reduced in the outer valence space. Meanwhile, the opposite energy shift trend is found in the intermediate valence space.

Keywords: electron momentum spectroscopy valence ionization energy charge density distribution

Received: 04 September 2011
Revised: 13 October 2011
Accepted manuscript online:

PACS:	34.50.-s	(Scattering of atoms and molecules)
	34.50.Gb	(Electronic excitation and ionization of molecules)
	34.80.-i	(Electron and positron scattering)
	34.80.Gs	(Molecular excitation and ionization)

Fund: Projects supported by the National Natural Science Foundation of China (Grant Nos. 10974139, 11104247, and 11176020).

Corresponding Authors: Yang Ze-Jin,zejinyang@yahoo.com.cn
E-mail: zejinyang@yahoo.com.cn

Cite this article:

Yang Ze-Jin(杨则金), Cheng Xin-Lu(程新路), Zhu Zheng-He(朱正和), and Yang Xiang-Dong(杨向东) Orbital responses to methyl sites in C_nH_2n+2 (n=1–6) 2012 Chin. Phys. B 21 023401

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Orbital responses to methyl sites in CnH2n+2 (n=1–6)

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Orbital responses to methyl sites in C_nH_2n+2 (n=1–6)