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Vibrational Spectroscopy of Hexahalo Complexes.

ABSTRACT: Halogenated inorganic complexes A_x[MHal_y] (A = alkali metal or alkaline earth, M = transition or main group metal, x = 1-3, and y = 2-9) are an archetypal class of compounds that provide entry points to large areas of inorganic and physical chemistry. All of the hexahalo complexes adopt an octahedral, O_h, symmetry (or nearly so). Consequently, one of the bending modes is forbidden in both the infrared and Raman spectra. In the solid state, many of the complexes crystallize in the cubic space group Fm3̅m, which preserves the octahedral symmetry. Even for those that are not cubic, the octahedral symmetry of the [MHal₆]^n- ion is largely retained and, to a good approximation, so are the selection rules. In the present work, we show that by using the additional information provided by neutron vibrational spectroscopy, in combination with conventional optical spectroscopies, we can generate complete and unambiguous assignments for all the modes. Comparison of the experimental and calculated transition energies for the systems where periodic-density functional theory was possible (i.e., those for which the crystal structure is known) shows that the agreement is almost quantitative. We also provide a linear relationship that enables the prediction of the forbidden mode.

SUBMITTER: Parker SF

PROVIDER: S-EPMC9171826 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

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Vibrational Spectroscopy of Hexahalo Complexes.

Parker Stewart F SF Williams Kenneth P J KPJ Smith Timothy T Ramirez-Cuesta Anibal J AJ Daemen Luke L LL

Inorganic chemistry 20220405 15

Halogenated inorganic complexes Ax[MHaly] (A = alkali metal or alkaline earth, M = transition or main group metal, x = 1-3, and y = 2-9) are an archetypal class of compounds that provide entry points to large areas of inorganic and physical chemistry. All of the hexahalo complexes adopt an octahedral, Oh, symmetry (or nearly so). Consequently, one of the bending modes is forbidden in both the infrared ...[more]

PMID: 35380803

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Project description:Vibrational spectroscopy is an essential tool in chemical analyses, biological assays, and studies of functional materials. Over the past decade, various coherent nonlinear vibrational spectroscopic techniques have been developed and enabled researchers to study time-correlations of the fluctuating frequencies that are directly related to solute-solvent dynamics, dynamical changes in molecular conformations and local electrostatic environments, chemical and biochemical reactions, protein structural dynamics and functions, characteristic processes of functional materials, and so on. In order to gain incisive and quantitative information on the local electrostatic environment, molecular conformation, protein structure and interprotein contacts, ligand binding kinetics, and electric and optical properties of functional materials, a variety of vibrational probes have been developed and site-specifically incorporated into molecular, biological, and material systems for time-resolved vibrational spectroscopic investigation. However, still, an all-encompassing theory that describes the vibrational solvatochromism, electrochromism, and dynamic fluctuation of vibrational frequencies has not been completely established mainly due to the intrinsic complexity of intermolecular interactions in condensed phases. In particular, the amount of data obtained from the linear and nonlinear vibrational spectroscopic experiments has been rapidly increasing, but the lack of a quantitative method to interpret these measurements has been one major obstacle in broadening the applications of these methods. Among various theoretical models, one of the most successful approaches is a semiempirical model generally referred to as the vibrational spectroscopic map that is based on a rigorous theory of intermolecular interactions. Recently, genetic algorithm, neural network, and machine learning approaches have been applied to the development of vibrational solvatochromism theory. In this review, we provide comprehensive descriptions of the theoretical foundation and various examples showing its extraordinary successes in the interpretations of experimental observations. In addition, a brief introduction to a newly created repository Web site (http://frequencymap.org) for vibrational spectroscopic maps is presented. We anticipate that a combination of the vibrational frequency map approach and state-of-the-art multidimensional vibrational spectroscopy will be one of the most fruitful ways to study the structure and dynamics of chemical, biological, and functional molecular systems in the future.

Dataset Information

Vibrational Spectroscopy of Hexahalo Complexes.

Publications

Vibrational Spectroscopy of Hexahalo Complexes.

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