Journal ArticleDOI
Accuracy and Interpretability: The Devil and the Holy Grail. New Routes across Old Boundaries in Computational Spectroscopy.
TLDR
This Review aims at being a comprehensive, authoritative, critical, and readable account of general interest to the chemistry community because of the wealth of qualitative and quantitative information that can be obtained from spectroscopic investigations.Abstract:
The past decade has witnessed an increasing interaction between experiment and theory in the field of molecular spectroscopy. On the computational side, ongoing developments of hardware and software have moved computational spectroscopy from a highly specialized research area to a general tool for researchers in different fields of chemical science. However, since its dawn, computational spectroscopy has been characterized by the dichotomies of qualitative and quantitative description, and of interpretation and accuracy. Indeed, the analysis of experiments is seldom straightforward because of the subtle interplay of several different effects, which are not easy to evaluate and isolate, and/or the complexity of the system under consideration. Often, the accuracy has to be set aside for a more qualitative analysis that will provide the means for a broad interpretation. In such a scenario, the most recent advances in theoretical treatments as well as computational tools have opened the way to the reconciliation of accuracy and interpretability, resulting in unequivocal analyses and assignments of experimental spectra and their unbiased interpretation. This Review aims at being a comprehensive, authoritative, critical, and readable account of general interest to the chemistry community because of the wealth of qualitative and quantitative information that can be obtained from spectroscopic investigations. Limiting ourselves to rotational and vibrational spectroscopy, emphasis will be put on accuracy and interpretability as well as on the routes toward their reconciliation and integration.read more
Citations
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Applications in stereochemical analysis of synthetic compounds, natural products, and biomolecules
TL;DR: Chiroptical spectroscopy and circular dichroism (CD) are increasingly important in all areas of chemistry, biochemistry, and structural biology as discussed by the authors, and the most widely used methods (electronic and vibrational CD) to frontier areas such as nonlinear spectroscopic and photoelectron CD are described.
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Perspective on integrating machine learning into computational chemistry and materials science
TL;DR: Machine learning (ML) methods are being used in almost every conceivable area of electronic structure theory and molecular simulation as mentioned in this paper and have become firmly established in the construction of high-dimensional interatomic potentials.
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Decoding chemical information from vibrational spectroscopy data: Local vibrational mode theory
Elfi Kraka,Wenli Zou,Yunwen Tao +2 more
TL;DR: The LMODEA software as mentioned in this paper performs the local vibrational mode analysis after a harmonic vibrational frequency calculation optionally using measured frequencies as additional input, which provides the highly sought after extension of the Badger rule to polyatomic molecules, and offers a simpler way to derive localized vibrations compared to the complex route via overtone spectroscopy.
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Vibrational optical activity for structural characterization of natural products.
TL;DR: This review presents the recent progress towards elucidating the structures of chiral natural products and applications using vibrational optical activity (VOA) spectroscopy, providing independent and complementary structural information.
Journal ArticleDOI
Computational molecular spectroscopy
Vincenzo Barone,Silvia Alessandrini,Malgorzata Biczysko,James R. Cheeseman,David C. Clary,Anne B. McCoy,Ryan J. DiRisio,Frank Neese,Mattia Melosso,Cristina Puzzarini +9 more
TL;DR: The Primer provides essential information about the characteristics, accuracy and limitations of current computational approaches used for modelling spectroscopic phenomena with a focus on estimating error bars, limitations and coupling interpretability to accuracy.
References
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Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
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Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
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VMD: Visual molecular dynamics
TL;DR: VMD is a molecular graphics program designed for the display and analysis of molecular assemblies, in particular biopolymers such as proteins and nucleic acids, which can simultaneously display any number of structures using a wide variety of rendering styles and coloring methods.
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A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
TL;DR: The revised DFT-D method is proposed as a general tool for the computation of the dispersion energy in molecules and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems.
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Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
TL;DR: In this paper, a detailed study of correlation effects in the oxygen atom was conducted, and it was shown that primitive basis sets of primitive Gaussian functions effectively and efficiently describe correlation effects.