Reactivity of tourmaline by quantum chemical calculations

Abstract

ZnAb initio calculations on reactivity of tourmaline were performed using both Gaussian and density function theory discrete variation method (DFT-DVM). The HF, B3LYP methods and basis sets STO-3G(3d,3p),6-31G(3d,3p) and 6-311++G(3df,3pd) were used in the calculations. The experimental results show energy value obtained from B3LYP and 6-31++1G(3df,3pd) basis sets is more accurate than those from other methods. The highest occupied molecular orbital (HOMO) of the tourmaline cluster mainly consists of O atom of hydroxyl group with relative higher energy level, suggesting that chemical bond between those of electron acceptor and this site may readily form, indicating the higher reactivity of hydroxyl group. The lowest unoccupied molecular orbital (LUMO) of the tourmaline cluster are dominantly composed of Si, O of tetrahedron and Na with relative lower energy level, suggesting that these atoms may tend to form chemical bond with those of electron donor. The results also prove that the O atoms of the tourmaline cluster have stronger reactivity than other atoms.

Keywords

DFT-DVM / tourmaline / quantum chemistry / surface reactivity

References

[1] Bershov M.J., Martirosyan V.O., Marfunin A.S. Color Centers in Lithium Tourmaline(elbaite)[J]. Sov. Phys.Crystallog, 1969, 13: 629

[2] krambrock K., Pinheiro M.V.B., Guedes K.J., Medeiros S. M., Schweizer S., Spaeth J. M. Correlation of Irradiation-induced Yellow Color with the O-hole Center in Tourmaline[J]. Phys. Chem. Minerals, 2004, 31: 168-175.

[3] Kubo. Interface Activity of Water Given Rise by Tourmaline[J]. Solid State Physics, 1989, 24: 12

[4] Hong H., Min X. Quantum Chemistry Mode Studying Mineral Surface Chemistry[M], 2004. WuHan: China University of Geosciences Press.

[5] Hong H., Tie L., Min X., Xiao R., Zhou Y., Bian Q. Surface Chemistry of Kaolinite by Quantum Chemistry Calculations[J]. Journal of Wuhan University of Technology, 2005, 27(1): 25-29.

[6] Labanowski J.K., Andzelm J.W. Density Functional Methods in Chemistry[M], 1991. New York: Springer Verlag.

[7] Xiao S., Wang C., Chen T.-lang. The Method of Density Function and Discrete Variation Used in Chemistry and Material Physics[M], 1998. Beijing: Science Press.

[8] Becke A.D. A New Mixing of Hartree-Fock and Local Density-Functional Theories[J]. J. Chem.Phys., 1993, 92: 1372-1377.

[9] Lee C.T., Yang W.T., Parr R.G. Development of the Colle-Salvetti Correlation-energy Formula into a Functional of Electrondensity[J]. Phys.Rev., 1988, B37: 785-789.

[10] Min X.-m., Hong H.-l., An J.-ming. Structure and Chemical Bond of Thermoelectric Ce-Co-Sb Skutterudites[J]. J.Wuhan Uni. Tech.-Mat. Sci. Ed., 2001, 16(1): 10-13.

[11] Min X., Xiao R., Wang H. Electronic Structure and Chemical Bond of Titanium Diboride[J]. J.Wuhan Uni. Tech.-Mat. Sci. Ed., 2003, 18(2): 11-14.

[12] Camara F., Ottolini L., Hawthorne F. C. Crystal Chemistry of Three Tourmalines by SREF, EMPA and SIMS[J]. American Mineralogist, 2000, 87: 1437-1442.

[13] Felipe M.A., Kubicki J.D., Rye D.M. Hydrogen Isotope Exchange Kinetics between H₂O and H₄SiO₄ from Ab Initio Calculations[J]. Geochimica et Cosmochimica Acta, 2003, 67(7): 1259-1276.

[14] Hehre W.J., Radom P.R., Pople J.A. Ab initio Molecular Orbital Theory[M], 1986. New York: Wiley.

[15] Tang Y., Wu R., Zhang X. The Mechanism of Applying Tourmaline to Purifying Cu²⁺ Doped Waste Water[J]. Acta Petrologica et Mineralogica, 2002, 21(2): 192-196.

[16] Zhang Z., Feng A., Guo Z. In Environment and Health Study of Spontaneous Polarization in Tourmaline[J]. China Non-Metallic Mining Industry Herald, 2003, 31: 47-49.

[17] Ji Z., Jin Z., Liang J., Wang J., Yan X. Influence of Tourmaline on pH Value of Water[J]. China Environmental Science, 2002, 22(6): 515-519.