Abstract
In this chapter, the quantum mechanical basis for computational studies of near-infrared spectra (NIR) is discussed. Since this topic is rarely covered in detail in the literature, the necessary prerequisites are provided as well, which include (i) the coordinate frame for the description of molecular vibrations, (ii) methods for the determination of the vibrational potential, (iii) the principles of the harmonic approximation, and (iv) its role as the foundation for methods taking anharmonic effects into account. The details of various anharmonic approaches in quantum vibrational spectroscopy are discussed, including methods based on the vibrational self-consistent field (VSCF) approach, vibrational perturbation theory (VPT) as well as one- and multidimensional grid-based methods. The merits and pitfalls of these approaches are critically assessed from the perspective of applications in NIR spectroscopy. Selected examples from recent literature are included to demonstrate how these methods can be applied to solve practical problems in spectroscopy. The aim of this chapter is to provide a comprehensive presentation of the topic aimed at a spectroscopic audience, while remaining accessible and focused on the key details. Although primarily intended for readers interested in NIR spectroscopy, the essential information provided in this chapter represents a fundamental perspective on quantum vibrational absorption spectroscopy and is useful for a more general readership as well.
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D.C. Harris, M.D. Bertolucci, Symmetry and spectroscopy. An Introduction to Vibrational and Electronic Spectroscopy (Dover Publications, INC., New York, 1980)
E.B. Wilson, J.C. Decius, P.C. Cross, Molecular Vibrations: The Theory of Infrared and Raman Vibrational Spectra (Dover Publications, INC., New York, 1980)
K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 6th edn. (Wiley, Hoboken, New Jersey, 2009)
F.S. Levin, An Introduction to Quantum Theory (Cambridge University Press, 2002)
P. Pulay, G. Fogarasi, F. Pong, J.E. Boggs, Systematic ab initio gradient calculation of molecular geometries, force constants, and dipole moment derivatives. J. Am. Chem. Soc. 101, 2550–2560 (1979)
T. Helgaker, P. Jorgensen, J. Olsen, Molecular Electronic—Structure Theory (Wiley, New York, 2000)
W. Koch, M.C. Holthausen, A Chemist’s Guide to Density Functional Theory, 2nd edn. (Wiley, VCH Verlag GmbH, 2001)
D.S. Sholl, J.A. Steckel, Density Functional Theory: A Practical Introduction, 1st edn (Wiley, 2009)
A.R. Leach, Molecular Modelling, 2nd edn. (Prentice Hall, Essex, 2001)
A. Stone, The Theory of Intermolecular Forces, 2nd edn. (Oxford University Press, Oxford, 2016)
F. Jensen, Introduction to Computational Chemistry, 3rd edn. (Wiley, Chichester, 2017)
T.K. Toy, R.B. Gerber, Vibrational self-consistent field calculations for spectroscopy of biological molecules: new algorithmic developments and applications. Phys. Chem. Chem. Phys. 15, 9468–9492 (2013)
M. Schmutzler, O.M.D. Lutz, C.W. Huck, Analytical pathway based on non-destructive NIRS for quality control of apples, in Infrared Spectroscopy: Theory, Developments and Applications, ed. by D. Cozzoliono (Nova Science Publisher, New York, USA, 2013)
J. Grabska, K.B. Beć, C.G. Kirchler, Y. Ozaki, C.W. Huck, Distinct difference in sensitivity of NIR vs. IR bands of melamine to inter-molecular interactions with impact on analytical spectroscopy explained by anharmonic quantum mechanical study. Molecules 24, 1402 (2019)
M.J. Schuler, T.S. Hofer, C.W. Huck, Assessing the predictability of anharmonic vibrational modes at the example of hydroxyl groups—ad hoc construction of localised modes and the influence of structural solute–solvent motifs. Phys. Chem. Chem. Phys. 19, 11990–12001 (2017)
K.B. Beć, J. Grabska, M.A. Czarnecki, Spectra-structure correlations in NIR region: spectroscopic and anharmonic DFT study of n-hexanol, cyclohexanol and phenol. Spectrochim. Acta A 197, 176–184 (2018)
U. Kuenzer, T.S. Hofer, A four-dimensional Numerov approach and its application to the vibrational eigenstates of linear triatomic molecules—the interplay between anharmonicity and inter-mode coupling. Chem. Phys. 520, 88–99 (2019)
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Beć, K.B., Grabska, J., Hofer, T.S. (2021). Introduction to Quantum Vibrational Spectroscopy. In: Ozaki, Y., Huck, C., Tsuchikawa, S., Engelsen, S.B. (eds) Near-Infrared Spectroscopy. Springer, Singapore. https://doi.org/10.1007/978-981-15-8648-4_5
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DOI: https://doi.org/10.1007/978-981-15-8648-4_5
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