13 Overview of Application of NIR Spectroscopy to Physical …
327
affected in different ways, which creates a rich source of information on molecular structure and interactions. For these exclusive values, NIR spectroscopy has
contributed remarkably to advancements accomplished in these fields over the last
three decades. On the other hand, because of extensive band overlapping, NIR spectra
are far more difficult for direct interpretation in comparison to fundamental transitions. Therefore, NIR spectroscopy in physicochemical research strongly depends on
advanced methods of spectra analysis, e.g. chemometrics or 2DCOS tools. In the
recent years, progress achieved in computational chemistry enabled the feasible simulation of NIR spectra by anharmonic quantum chemical calculations. This development dramatically increases the level of detail in band assignments, enables to follow
up on fine spectral effects and to ascribe them to structural changes occurring at the
molecular scale. Still, large molecules or some effects that are delocalized over a
volume of the sample presently remain inaccessible for computational approaches
due to the prohibitive cost associated to the anharmonic treatment. However, once
these practical limitations are overcome, new insights, e.g. into solvent effects, molecular dynamics in large interacting systems, polymer properties, etc., can be achieved.
With the continued progress in technology and quantum theory in the near future,
it may be anticipated that the research focus in NIR spectroscopy will be strongly
influenced in the coming years as well.
References
1. V. Barone, M. Biczysko, J. Bloino, M. Borkowska-Panek, I. Carnimeo, P. Panek, Toward
anharmonic computations of vibrational spectra for large molecular systems. Int. J. Quantum
Chem. 112, 2185–2200 (2012)
2. T. Gonjo, Y. Futami, Y. Morisawa, M.J. Wójcik, Y. Ozaki, Hydrogen bonding effects on the
wavenumbers and absorption intensities of the OH fundamental and the first, second, and third
overtones of phenol and 2,6-dihalogenated phenols studied by visible/near-infrared/infrared
spectroscopy. J. Phys. Chem. A 115, 9845–9853 (2011)
3. K.B. Be´ c, J. Grabska, C.W. Huck, Y. Ozaki, Quantum mechanical simulation of near-infrared
spectra. Applications in physical and snalytical chemistry. in Molecular Spectroscopy: A
Quantum Chemistry Approach. ed by Y. Ozaki, M.J. Wójcik, J. Popp, (Weinheim, Grermany,
Wiley-VCH, 2019) pp. 353–388
4. K.B. Be´ c, C.W. Huck, Breakthrough potential in near-infrared spectroscopy: spectra simulation.
A review of recent developments. Front. Chem. 7, 48 (2019)
5. M.A. Czarnecki, Y. Morisawa, Y. Futami, Y. Ozaki, Advances in molecular structure and
interaction studies using near-infrared spectroscopy. Chem. Rev. 115, 9707–9744 (2015)
6. L. Bokobza, Origin of near-infrared absorption bands. in Near-Infrared Spectroscopy: Principles, Instruments, Applications, ed. by H.W. Siesler, Y. Ozaki, S. Kawata, H.M. Heise,
(Wiley-VCH Verlag GmbH, 2002), pp. 11–42
7. B.R. Henry, Use of local modes in the description of highly vibrationally excited molecules.
Acc. Chem. Res. 20, 429–435 (1987)
8. H.G. Kjaergaard, H. Yu, B.J. Schattka, B.R. Henry, A.W. Tarr, Intensities in local mode overtone
spectra: Propane. J. Chem. Phys. 93, 6239–6248 (1990)
9. Y. Chen, Y. Morisawa, Y. Futami, M.A. Czarnecki, H.S. Wang, Y. Ozaki, Combined IR/NIR
and density functional theory calculations analysis of the solvent effects on frequencies and
intensities of the fundamental and overtones of the C=O stretching vibrations of acetone and
2-hexanone. J. Phys. Chem. A 118, 2576–2583 (2014)
327
affected in different ways, which creates a rich source of information on molecular structure and interactions. For these exclusive values, NIR spectroscopy has
contributed remarkably to advancements accomplished in these fields over the last
three decades. On the other hand, because of extensive band overlapping, NIR spectra
are far more difficult for direct interpretation in comparison to fundamental transitions. Therefore, NIR spectroscopy in physicochemical research strongly depends on
advanced methods of spectra analysis, e.g. chemometrics or 2DCOS tools. In the
recent years, progress achieved in computational chemistry enabled the feasible simulation of NIR spectra by anharmonic quantum chemical calculations. This development dramatically increases the level of detail in band assignments, enables to follow
up on fine spectral effects and to ascribe them to structural changes occurring at the
molecular scale. Still, large molecules or some effects that are delocalized over a
volume of the sample presently remain inaccessible for computational approaches
due to the prohibitive cost associated to the anharmonic treatment. However, once
these practical limitations are overcome, new insights, e.g. into solvent effects, molecular dynamics in large interacting systems, polymer properties, etc., can be achieved.
With the continued progress in technology and quantum theory in the near future,
it may be anticipated that the research focus in NIR spectroscopy will be strongly
influenced in the coming years as well.
References
1. V. Barone, M. Biczysko, J. Bloino, M. Borkowska-Panek, I. Carnimeo, P. Panek, Toward
anharmonic computations of vibrational spectra for large molecular systems. Int. J. Quantum
Chem. 112, 2185–2200 (2012)
2. T. Gonjo, Y. Futami, Y. Morisawa, M.J. Wójcik, Y. Ozaki, Hydrogen bonding effects on the
wavenumbers and absorption intensities of the OH fundamental and the first, second, and third
overtones of phenol and 2,6-dihalogenated phenols studied by visible/near-infrared/infrared
spectroscopy. J. Phys. Chem. A 115, 9845–9853 (2011)
3. K.B. Be´ c, J. Grabska, C.W. Huck, Y. Ozaki, Quantum mechanical simulation of near-infrared
spectra. Applications in physical and snalytical chemistry. in Molecular Spectroscopy: A
Quantum Chemistry Approach. ed by Y. Ozaki, M.J. Wójcik, J. Popp, (Weinheim, Grermany,
Wiley-VCH, 2019) pp. 353–388
4. K.B. Be´ c, C.W. Huck, Breakthrough potential in near-infrared spectroscopy: spectra simulation.
A review of recent developments. Front. Chem. 7, 48 (2019)
5. M.A. Czarnecki, Y. Morisawa, Y. Futami, Y. Ozaki, Advances in molecular structure and
interaction studies using near-infrared spectroscopy. Chem. Rev. 115, 9707–9744 (2015)
6. L. Bokobza, Origin of near-infrared absorption bands. in Near-Infrared Spectroscopy: Principles, Instruments, Applications, ed. by H.W. Siesler, Y. Ozaki, S. Kawata, H.M. Heise,
(Wiley-VCH Verlag GmbH, 2002), pp. 11–42
7. B.R. Henry, Use of local modes in the description of highly vibrationally excited molecules.
Acc. Chem. Res. 20, 429–435 (1987)
8. H.G. Kjaergaard, H. Yu, B.J. Schattka, B.R. Henry, A.W. Tarr, Intensities in local mode overtone
spectra: Propane. J. Chem. Phys. 93, 6239–6248 (1990)
9. Y. Chen, Y. Morisawa, Y. Futami, M.A. Czarnecki, H.S. Wang, Y. Ozaki, Combined IR/NIR
and density functional theory calculations analysis of the solvent effects on frequencies and
intensities of the fundamental and overtones of the C=O stretching vibrations of acetone and
2-hexanone. J. Phys. Chem. A 118, 2576–2583 (2014)