Funda Altınkaynak, Mehmet Fatih Kaya, Gürkan Keşan, Cemal Parlak

[PtX4]2- (X = Cl ve Br) İYONLARININ TİTREŞİM FREKANSLARININ TEORİK OLARAK İNCELENMESİ

[PtX4]2- (X = Cl ve Br) iyonlarının normal mod frekansları ve bunlara karşılık gelen titreşim işaretlemeleri standart kuantum kimyasal teknikler ile teorik olarak incelenmektedir. Tüm normal modlar [PtX4]2- iyonunun D4h nokta grubu kullanılarak başarılı bir şekilde işaretlenmektedir. Hesaplamalar Lanl2dz baz seti kullanılarak B3LYP yoğunluk fonksiyonel metoduyla gerçekleştirilmiştir. İnfrared şiddetleri ile Raman aktiviteleri de hesaplanmaktadır. Teorik sonuçlar mevcut deneysel değerler ile başarılı bir şekilde karşılaştırılmaktadır.

Anahtar Kelimeler:

Titreşim işaretlemesi, Normal mod frekansı, B3LYP, Lanl2dz

THEORETICAL INVESTIGATION OF VIBRATIONAL FREQUENCIES OF [PtX4]2- (X = Cl and Br) IONS

The normal mode frequencies and corresponding vibrational assignments of [PtX4]2- (X = Cl and Br) ions have been theoretically examined by means of standard quantum chemical techniques. All normal modes are successfully assigned utilizing the D4h symmetry of [PtX4]2-. Calculations have been performed at the Becke-3-Lee-Yang-Parr (B3LYP) density functional method using the Lanl2dz basis set. Infrared intensity and Raman activities are also calculated and reported. Theoretical results are successfully compared to available experimental data.

Keywords:

Vibrational assignment, Normal mode frequency, B3LYP, Lanl2dz,

PDF

___

[1] K. Nakamoto, ‘‘Infrared and Raman spectra of inorganic and coordination compounds’’, Wiley, New York, pp. 141-145, (1986).
[2] R.C. Jones, B.W. Skelton, V.A. Tolhurst, A.H. White, A.J. Wilson, A.J. Canty, ‘‘Synthesis and solid state structural characterization of Pt(II,IV) bromide complexes containing bidentate organothiomethylpyridine heteroleptic ligands’’, Polyhedron 26: 708, (2007).
[3] K. Sakai, Y. Tomita, T. Ue, K. Goshima, M. Ohminato, T. Tsubomura, K. Matsumoto, K. Ohmura, K. Kawakami, ‘‘Syntheses, antitumor activity, and molecular mechanics studies of cis-PtCl2(pzH)2 (pzH_pyrazole) and related complexes. Crystal structure of a novel Magnus-type double-salt [Pt(pzH)4][PtCl4][cis-PtCl2(pzH)2]2 involving two perpendicularly aligned 1D chains’’, Inorg. Chimica Acta 297: 64, (2000).
[4] J.S. Casas, A. Castineiras, Y. Parajo, A. Sanchez, A.S. Gonzalez, J. Sordo, ‘‘Synthesis and cytotoxicity of new Pt(IV) complexes of 2,20-biimidazole and derivatives’’, Polyhedron 24: 1196, (2005).
[5] C.E. Check, T.O. Faust, J.M. Bailey, B.J. Wright, T.M. Gilbert, L.S. Sunderlin, ‘‘Addition of polarization and diffuse functions to the Lanl2dz basis set for P-block elements’’, Journal of Physical Chemistry A, 105: 8111, (2001).
[6] I. Bytheway, M.W. Wong, ‘‘The prediction of vibrational frequencies of inorganic molecules using density functional theory’’, Chem. Phys. Lett. 282: 219, (1998).
[7] C. Parlak, “Theoretical and experimental vibrational spectroscopic study of 4-(1-Pyrrolidinyl)piperidine”, J. Mol. Struct. 966: 1, (2010).
[8] Ö. Alver, C. Parlak, ‘‘DFT, FT-Raman, FT-IR, liquid and solid state NMR studies of 2,6-dimethoxyphenyl-boronic acid’’, Vibrational Spectroscopy, 54: 1, (2010).
[9] P.J. Hay and W.R. Wadt, ‘‘Ab initio effective core potentials for molecular calculations, Potentials for K to Au including the outermost core orbitals’’, J. Chem. Phys. 82: 299, (1985).
[10] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, ‘‘Gaussian 09 Revision A.01’’, (2009).
[11] R.D. Dennington, T. A. Keith, J. M. Millam, ‘‘GaussView 5.0.8’’, Gaussian Inc., (2008).