Vibrational dynamics of acetate in D2O studied by infrared pump–probe spectroscopy

Literature Information

Publication Date 2012-02-01
DOI 10.1039/C2CP23647H
Impact Factor 3.676
Authors

Motohiro Banno, Keisuke Tominaga


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Abstract

Solute–solvent interactions between acetate and D2O were investigated by vibrational spectroscopic methods. The vibrational dynamics of the COO asymmetric stretching mode in D2O was observed by time-resolved infrared (IR) pump–probe spectroscopy. The pump–probe signal contained both decay and oscillatory components. The time dependence of the decay component could be explained by a double exponential function with time constants of 200 fs and 2.6 ps, which are the same for both the COO asymmetric and symmetric stretching modes. The Fourier spectrum of the oscillatory component contained a band around 80 cm−1, which suggests that the COO asymmetric stretching mode couples to a low-frequency vibrational mode with a wavenumber of 80 cm−1. Based on quantum chemistry calculations, we propose that a bridged complex comprising an acetate ion and one D2O molecule, in which the two oxygen atoms in the acetate anion form hydrogen bonds with the two deuterium atoms in D2O, is the most stable structure. The 80 cm−1 low-frequency mode was assigned to the asymmetric stretching vibration of the hydrogen bond in the bridged complex.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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