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On the Accuracy of the Complete Basis Set Extrapolation for Anionic Systems: A Case Study of the Electron Affinity of Methane

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DOI: 10.4236/cc.2014.22005    5,667 Downloads   9,495 Views   Citations

ABSTRACT

Recent experimental evidence suggests again the existence of the metastable methane anion in plasma swarms. In order to test the reliability of the complete basis set (CBS) extrapolation scheme with augmented correlation-consistent basis sets for anionic molecules, we study the evolution of the electron affinity of methane with benchmark ab initio calculations with aug-cc basis sets up to aug-cc-pV6Z + diffuse. Geometry optimizations and vibrational analysis were done at the MP2 level. The electron affinity (EA) was calculated at the MP2 and CCSD(T) levels with and without frozen core and including the extrapolations to the CBS limit. Using the aug-cc-pVnZ basis sets it is found that two non-decreasing CCSD(T) CBS limits exist for the EA (0.29 and 0.53 eV) obtained with the n = 3, 4, 5 and n = 4, 5, 6 series, respectively. A new scheme is proposed which can be generalized for very accurate quantum chemical description of molecular anions: the standard aug-cc-pVnZ basis sets can be supplemented with extra-diffuse orbitals using a simple even-tempered scheme. This yields a reliable CBS extrapolation method to develop a (discrete approximation of a) continuum anionic state near ionization, viz., one that closely matches the energy of the corresponding neutral state. These results show that CH4 has no stable anions of 2A1 symmetry, implying that plasma swarms with anionic methane consist of metastable rather than stable methane anions.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

Ramírez-Solís, A. (2014) On the Accuracy of the Complete Basis Set Extrapolation for Anionic Systems: A Case Study of the Electron Affinity of Methane. Computational Chemistry, 2, 31-41.
doi: 10.4236/cc.2014.22005.

References

[1] Trepka, L.V. and Neurt, H. (1963) Uberdie Entstehung von Negativen Ionen. Zeitschrift für Naturforschung A, 18, 1295.
[2] Sharp, T.E. and Dowell, J.T. (1967) Isotope Effects in Dissociative Attachment of Electrons in Methane. The Journal of Chemical Physics, 46, 1530. http://dx.doi.org/10.1063/1.1840885
[3] Hunter, S.R., Carter, J.G. and Christophorou, L.G. (1986) Electron Transport Measurements in Methane Using an Improved Pulsed Townsend Technique. Journal of Applied Physics, 60, 24.
http://dx.doi.org/10.1063/1.337690
[4] Bordage, M.C. (1995) Thèse de Doctorat. Université Paul Sabatier de Toulouse, France.
[5] de Urquijo, J., Arriaga, C.A., Cisneros, C. and Alvarez, I. (1999) A Time-Resolved Study of Ionization, Electron Attachment and Positive-Ion Drift in Methane. Journal of Physics D: Applied Physics, 32, 41.
http://dx.doi.org/10.1088/0022-3727/32/1/008
[6] de Urquijo, J., Herrera, J. and Private Communication (2014)
[7] CRC Handbook of Chemistry and Physics 1986-1987, Vol. 47. CRC Press, Boca Raton.
[8] Hernández, E.M., Hernández, L., Martílnez-Flores, C., Trujillo, N., Salazar, M., Chávez, A. and Hinojosa, G. (2014) Electron Detachment cross Sections of CH4- Colliding with O2 and N2 below 10 kEV. Plasma Sources Science and Technology, 23, Article ID: 015018.
http://dx.doi.org/10.1088/0963-0252/23/1/015018
[9] Jursic, B.S. (2000) Theoretical Investigation of Structures and Energies of the Protonated Methane Radical Cation and Ethane. Journal of Molecular Structure: THEOCHEM, 498, 149. http://dx.doi.org/10.1016/S0166-1280(99)00254-7
[10] Montgomery, J.A., Ochterski, J.W. and Petersson, G.A. (1994) A Complete Basis Set Model Chemistry. IV. An Improved Atomic Pair Natural Orbital Method. The Journal of Chemical Physics, 101, 5900.
http://dx.doi.org/10.1063/1.467306
[11] Pople, J.A., Head-Gordon, M., Fox, D.J., Raghavachari, K., Curtiss, L.A. (1989) Gaussian-1 Theory: A General Procedure for Prediction of Molecular Energies. The Journal of Chemical Physics, 90, 5622.
http://dx.doi.org/10.1063/1.456415
[12] Raghavachari, K., Trucks, G.W. and Pople, J.A. (1991) Electronic Structures of the Negative Ions Si¯2 –Si¯ 10: Electron Affinities of Small Silicon Clusters. The Journal of Chemical Physics, 94, 7221.
http://dx.doi.org/10.1063/1.459738
[13] Curtiss, L.A., Raghavachari, K. and Pople, J.A. (1993) Gaussian-2 Theory Using Reduced MÖller-Plesset Orders. The Journal of Chemical Physics, 98, 1293. http://dx.doi.org/10.1063/1.464297
[14] Dunning, T.H. (1989) Gaussian Basis Sets for Use in Correlated Molecular Calculations. I. The Atoms Boron through Neon and Hydrogen. The Journal of Chemical Physics, 90, 1007.
http://dx.doi.org/10.1063/1.456153
[15] Temelso, B., Valeev, E.F. and Sherrill, C.D. (2004) A Comparison of One-Particle Basis Set Completeness, Higher-Order Electron Correlation, Relativistic Effects, and Adiabatic Corrections for Spectroscopic Constants of BH, CH+, and NH+. The Journal of Chemical Physics A, 108, 3068.
http://dx.doi.org/10.1021/jp036933+
[16] Wilson, A.K., van Mourik, T. and Dunning Jr., T.H. (1997) Gaussian Basis Sets for Use in Correlated Molecular Calculations. VI. Sextuple Zeta Correlation Consistent Basis Sets for Boron through Neon. Journal of Molecular Structure: THEOCHEM, 388, 339; aug-cc-pVnZ basis sets from https://bse.pnl.gov/bse/portal
http://dx.doi.org/10.1016/S0166-1280(96)80048-0
[17] Frisch, M.J., Trucks, G.W., Schlegel, H.B., et al. (2009) Gaussian 09, Gaussian Inc., Pittsburgh.
[18] Peterson, K.A., Woon, D.E. and Dunning Jr., T.H. (1994) Benchmark Calculations with Correlated Molecular Wave Functions. IV. The Classical Barrier Height of the H+H2→H2+H Reaction. The Journal of Chemical Physics, 100, 7410. http://dx.doi.org/10.1063/1.466884
[19] Feller, D. and Sordo, J.A. (2000) A CCSDT Study of the Effects of Higher Order Correlation on Spectroscopic Constants. I. First Row Diatomic Hydrides. The Journal of Chemical Physics, 112, 5604.
http://dx.doi.org/10.1063/1.481135
[20] de Lara-Castells, M.P., Krems, R.V., Buchachenko, A.A., Delgado-Barrio, G. and Villarreal, P. (2001) Complete Basis Set Extrapolation Limit for Electronic Structure Calculations: Energetic and Nonenergetic Properties of HeBr and HeBr2 (with 2 as Subscript) van der Waals Dimers. The Journal of Chemical Physics, 115, 10438. http://dx.doi.org/10.1063/1.481135
[21] Schulz, G.J. (1973) Resonances in Electron Impact on Diatomic Molecules. Reviews of Modern Physics, 45, 423. http://dx.doi.org/10.1103/RevModPhys.45.423

  
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