İzonitrosoasetofenon Molekülünün Titreşimlerinin Analizi

Abstract

Bu çalışmada izonitrosoasetofenon molekülünün deneysel olarak ölçülen titreşim frekansları ile teorik olarak hesaplanmış titreşim frekanslarının uyumu incelenmiştir. Molekülün geometri optimizasyonu ve titreşim frekansı hesaplamaları ab initio metotları kullanılarak yapılmıştır. Teorik hesaplamalarda DFT-B3LYP metoduyla 6-311++G(d,p) ve 6-31G(d) baz setleri, HF metoduyla 6-31G(d) baz seti kullanılmıştır. Hesaplanmış titreşim frekansları kaynak [1,12] den alınan düzeltme çarpanlarıyla yeniden düzenlenmiştir. Düzenlenen frekansların deneyle daha iyi uyum içerisinde olduğu görülmüştür. Aynı zamanda bu çalışmada kullanılan metot ve baz setlerinin performansı da incelenmiş, DFT-B3LYP metoduyla kullanılan 6-311++G(d,p) baz setinin titreşim frekansı hesabında en iyi performansı sergilediği bulunmuştur.

Keywords

• Titreşim Spektroskopisi, Frekans hesaplamaları, ab initio metotları

Vibrational Analysis of Isonitrosoacetophenone Molecule

Abstract

In this study, the agreement between the experimental and calculated vibrational frequencies of isonitrosoasetophenon was investigated. The geometrical optimization and vibrational frequency calculations of the molecule were carried out by using ab initio methods. 6-31G(d) and 6-311++G(d,p) basis sets were used with DFTB3LYP method and 6-31 G(d) basis set was used with HF method for theoretical calculations. Calculated vibrational frequencies were scaled with scale factors obtained from ref.[1,12]. It was found that scaled vibrational frequencies are in good agreement with the experimental data. And also the performance of the methods and basis sets, which were used in this study, was investigated. It was found that DFT-B3LYP method with 6-311++G(d,p) basis set is the most succesfull procedure for frequency calculations.

Keywords

• Vibrational spectroscopy, Frequency calculations, ab initio methods

References

1. [1] Akalın, E., Yılmaz,A., Akyüz, S., Vibrational Analysis of Isonicotinamide, J. Mol. Struct., 744-747, 881-886 (2005)
2. [2] Bolukbasi, O., Akyuz, S., Computational Vibrational Study on Coordinated Nicotinamide, J. Mol. Struct., 744-747, 961-971 (2005)
3. [3] Dimitrova, Y., Tsenov, J.A., Ab initio and DFT studies of the structure, stability and vibrational spectrum of the hydrogen-bonded (CH3)2O…HONO2 complex , J. Mol. Struct. (Theochem), 683, 65- 70 (2004)
4. [4] Dimitrova, Y., Theoretical study of the structures, stability and vibrational spectra of the nitrous acid complexes with CH4, Spectrochim. Acta Part A, 60, 2163-2170 (2004)
5. [5] Pulay, P., Fogarasi, G., Zhou, X., Taylor, P.W., Ab initio prediction of vibrational spectra: A database approach , Vib. Spectrosc, 1, 159-165 (1990)
6. [6] Kalincsak, F., Pongor, G., An experimental and theoretical study of vibrational spectra of picolinamide, nicotinamide, and isonicotinamide, Spectrochim. Acta Part A, 58, 99–1011 (2002)
7. [7] Ozel, A.E., and Akyuz, S., Vibrational Assignment,ab-initio Calculation and Normal Coordinate Analysis of 2,2’-Biquinoline, J. Struct. Chem., 46, 1077-1081 (2005)
8. [8] Krishnakumar, V., Surumbarkuzhali, N., Analysis of structure and vibrational spectra of 2,5- dihydroxybenzoicacid based on density functional theory calculations, J. Raman Spectrosc., 41, 473-478 (2009)

9. [9] Ferreira, G. B., Hollauer, E., Comerlato, N. M., Wardell, J.L., An experimental and theoretical vibrational spectroscopic study of [AsPh4]2[Sn(dmit)3]·Me2CO, Spectrochim Acta, Part A, 62, 681- 689 (2005)
10. [10] Kuznetsov, M. L., Dement'ev, A. I., Nazarov, A. A. Theoretical analysis of the vibrational spectra and the nature of the coordination bond of platinum nitrile complexes , Russ. J. Inorg. Chem., 50, 731-739 (2005)
11. [11] Singh, R.B., Garg, B.S., Singh, R.P., Oximes as Spectrophotometric Reagents-A Review, Tetrahedron, 26, 425-44 (1979)
12. [12] Scott, A.P., Radom, L. , Harmonic Vibrational Frequencies: An Evaluation of Hartree−Fock, Møller−Plesset, Quadratic Configuration Interaction, Density Functional Theory, and Semiempirical Scale Factors, J.Phys.Chem., 100, 16502–16513 (1996)
13. [13] Thakkar, N.V., Haldar, B.C., Magnetic and spectral studies of complexes of isonitrosoacetophenone (HINAP) with Ni(II), Pd(II) and Pt(II) , J. Inorg. Nucl. Chem., 42, 843-849 (1980)
14. [14] Güp, R., Koç, Z., Synthesis and investigation extraction properties of 4- methylacetophenone, 4- chloroacetophenone and isonitrosoacetephenone 4-aminobenzoylhydrazones, S.Ü. Fen Fak. Fen Dergisi, 23, 15-19 (2004)
15. [15] Güp, R., Giziroğlu, E., Metal complexes and solvent extraction properties isonitrosoacetophenone 2-aminobenzoylhydrazone , Spectrochim. Acta Part A, 65, 719-726 (2006)
16. [16] Bilgiçataç, H.N., Glioksim veya Aminoglioksim Türevlerinin Sentezi ve Bazı Geçiş Metal Komplekslerinin İncelenmesi , Doktora Tezi , U.Ü. Fen Bilimleri Enstitüsü, Bursa (2006)