Anharmonicities and coherent vibrational dynamics of phosphate ions in bulk H2O

文献信息

发布日期 2015-10-01
DOI 10.1039/C5CP04502A
影响因子 3.676
作者

Rene Costard, Tobias Tyborski, Benjamin P. Fingerhut


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摘要

Phosphates feature prominently in the energetics of metabolism and are important solvation sites of DNA and phospholipids. Here we investigate the ion H2PO4− in aqueous solution combining 2D IR spectroscopy of phosphate stretching vibrations in the range from 900–1300 cm−1 with ab initio calculations and hybrid quantum-classical molecular dynamics based simulations of the non-linear signal. While the line shapes of diagonal peaks reveal ultrafast frequency fluctuations on a sub-100 fs timescale caused by the fluctuating hydration shell, an analysis of the diagonal and cross-peak frequency positions allows for extracting inter-mode couplings and anharmonicities of 5–10 cm−1. The excitation with spectrally broad pulses generates a coherent superposition of symmetric and asymmetric PO2− stretching modes resulting in the observation of a quantum beat in aqueous solution. We follow its time evolution through the time-dependent amplitude and the shape of the cross peaks. The results provide a complete characterization of the H2PO4− vibrational Hamiltonian including fluctuations induced by the native water environment.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 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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