Exploring the Absorption Spectrum of Simulated Water from MHz to Infrared
Exploring the Absorption Spectrum of Simulated Water from MHz to Infrared
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DOI：
10.1021/acs.jpca.0c04063
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发表时间：
2020-07-09
影响因子：
2.9
通讯作者：
Netz, Roland R.
中科院分区：
文献类型：
--
作者：
Carlson, Shane;Bruenig, Florian N.;Netz, Roland R.
从经典和密度泛函理论分子动力学模拟数据计算了液态水在300 K下的吸收光谱，这些数据的范围从1 MHz到数百THz，在整个范围内，包括IR模式，微波峰和中间THz波段，定性和定量地与实验数据一致。光谱被分解成单分子和集体组件，以及由于分子重新取向和诱导分子偶极矩的变化的组件。这些分解揭示了在20和5太赫兹，分别为基础的librational和平移（氢键拉伸）带的运动;供体质子和受体孤对电子之间的相互作用被证明是重要的线的形状在librational和平移制度，和在和出的相librational二聚体模式进行观察和探索。
Absorption spectra of liquid water at 300 K are calculated from both classical and density functional theory molecular dynamics simulation data, which together span from 1 MHz to hundreds of THz, agreeing well with experimental data qualitatively and quantitatively over the entire range, including the IR modes, the microwave peak, and the intermediate THz bands. The spectra are decomposed into single-molecular and collective components, as well as into components due to molecular reorientations and changes in induced molecular dipole moments. These decompositions shed light on the motions underlying the librational and translational (hydrogen-bond stretching) bands at 20 and 5 THz, respectively; interactions between donor protons and acceptor lone pair electrons are shown to be important for the line shape in both librational and translational regimes, and in- and out-of-phase librational dimer modes are observed and explored.