Scaling Procedures in Vibrational Spectroscopy

Bąk, Olga; Borowski, Piotr

doi:10.1007/978-3-030-01355-4_2

Cited by 3 publications

(2 citation statements)

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“…Mode‐specific scaling of force constants have been investigated extensively, as reviewed by Bąk and Borowski 43 and Palafox 42 . Improved prediction accuracy can be obtained (e.g., RMSE below 15 cm −1 ); however, their complexity and reliance on available benchmark data for the considered mode limits routine applications in quantum chemistry calculations.…”

Section: History Of Uniform Scaling Factorsmentioning

confidence: 99%

“…Different strategies involving scaling factors have been proposed to addressed the overestimation in the calculated harmonic frequencies (as reviewed by Palafox 42 and Bąk and Borowski 43 ). However, global uniform multiplicative scaling factors (hereafter just uniform scaling factors) have become the most popular approach to produce scaled harmonic (predicted fundamental) frequencies that can be directly compared with experimental fundamental frequencies.…”

Section: Introductionmentioning

confidence: 99%

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Meta‐analysis of uniform scaling factors for harmonic frequency calculations

Trujillo

McKemmish

2021

WIREs Comput Mol Sci

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Vibrational frequency calculations performed under the harmonic approximation are widespread across chemistry. However, it is well‐known that the calculated harmonic frequencies tend to systematically overestimate experimental fundamental frequencies; a limitation commonly overcome with multiplicative scaling factors. In practice, multiplicative scaling factors are derived for each individual model chemistry choice (i.e., a level of theory and basis set pair), where performance is judged by, for example, the root‐mean square error (RMSE) between the predicted scaled and experimental frequencies. However, despite the overwhelming number of scaling factors reported in the literature and model chemistry approximations available, there is little guidance for users on appropriate model chemistry choices for harmonic frequency calculations. Here, we compile and analyze the data for 1495 scaling factors calculated using 141 levels of theory and 109 basis sets. Our meta‐analysis of this data shows that scaling factors and RMSE approach convergence with only hybrid functionals and double‐zeta basis sets, with anharmonicity error already dominating model chemistry errors. Noting inconsistent data and the lack of independent testing, we can nevertheless conclude that a minimum error of 25 cm−1—arising from insufficiently accurate treatment of anharmonicity—is persistent regardless of the model chemistry choice. Based on the data we compiled and cautioning the need for a future systematic benchmarking study, we recommend ωB97X‐D/def2‐TZVP for most applications and B2PLYP/def2‐TZVPD for superior intensity predictions. With a smaller benchmark set, direct comparison prefers ωB97X‐D/6‐31G* to B3LYP/6‐31G*. This article is categorized under: Electronic Structure Theory > Density Functional Theory Theoretical and Physical Chemistry > Spectroscopy

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Section: History Of Uniform Scaling Factorsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Meta‐analysis of uniform scaling factors for harmonic frequency calculations

Trujillo

McKemmish

2021

WIREs Comput Mol Sci

View full text Add to dashboard Cite

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Decoding chemical information from vibrational spectroscopy data: Local vibrational mode theory

Kraka

Zou

Tao

2020

WIREs Comput Mol Sci

107

205

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Modern vibrational spectroscopy is more than just an analytical tool. Information about the electronic structure of a molecule, the strength of its bonds, and its conformational flexibility is encoded in the normal vibrational modes. On the other hand, normal vibrational modes are generally delocalized, which hinders the direct access to this information, attainable only via local vibration modes and associated local properties. Konkoli and Cremer provided an elegant solution to this problem by deriving local vibrational modes from the fundamental normal modes, obtained in the harmonic approximation of the potential, via mass-decoupled Euler-Lagrange equations. This review gives a general introduction into the local vibrational mode theory of Konkoli and Cremer and elucidates how this theory unifies earlier attempts to obtain easy to interpret chemical information from vibrational spectroscopy: i) the local mode theory furnishes bond strength descriptors derived from force constant matrices with a physical basis, ii) provides the highly sought after extension of the Badger rule to polyatomic molecules, iii) and offers a simpler way to derive localized vibrations compared to the complex route via overtone spectroscopy. Successful applications are presented, including a new measure of bond strength, a new detailed analysis of IR/Raman spectra, and the recent extension to periodic systems, opening a new avenue for the characterization of bonding in crystals. At the end of this review the LMODEA software is introduced, which performs the local mode analysis (with minimal computational costs) after a harmonic vibrational frequency calculation or by using measured frequencies as input.

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The Local Vibrational Mode Theory and Its Place in the Vibrational Spectroscopy Arena

et al. 2022

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This Feature Article starts highlighting some recent experimental and theoretical advances in the field of IR and Raman spectroscopy, giving a taste of the breadth and dynamics of this striving field. The local mode theory is then reviewed, showing how local vibrational modes are derived from fundamental normal modes. New features are introduced that add to current theoretical efforts: (i) a unique measure of bond strength based on local mode force constants ranging from bonding in single molecules in different environments to bonding in periodic systems and crystals and (ii) a new way to interpret vibrational spectra by pinpointing and probing interactions between particular bond stretching contributions to the normal modes. All of this represents a means to work around the very nature of normal modes, namely that the vibrational motions in polyatomic molecules are delocalized. Three current focus points of the local mode analysis are reported, demonstrating how the local mode analysis extracts important information hidden in vibrational spectroscopy data supporting current experiments: (i) metal−ligand bonding in heme proteins, such as myoglobin and neuroglobin; (ii) disentanglement of DNA normal modes; and (iii) hydrogen bonding in water clusters and ice. Finally, the use of the local mode analysis by other research groups is summarized. Our vision is that in the future local mode analysis will be routinely applied by the community and that this Feature Article serves as an incubator for future collaborations between experiment and theory.

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Scaling Procedures in Vibrational Spectroscopy

Cited by 3 publications

References 74 publications

Meta‐analysis of uniform scaling factors for harmonic frequency calculations

Meta‐analysis of uniform scaling factors for harmonic frequency calculations

Decoding chemical information from vibrational spectroscopy data: Local vibrational mode theory

The Local Vibrational Mode Theory and Its Place in the Vibrational Spectroscopy Arena

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