Reinvestigation of the Infrared Spectrum of the Gas-Phase Protonated Water Tetramer

被引:25
作者
Wang, Huan [1 ]
Agmon, Noam [1 ]
机构
[1] Hebrew Univ Jerusalem, Inst Chem, Fritz Haber Res Ctr, IL-91904 Jerusalem, Israel
基金
以色列科学基金会;
关键词
AB-INITIO CALCULATIONS; MOLECULAR-DYNAMICS; POTENTIAL-ENERGY; HYDRATED PROTON; CLUSTER IONS; VIBRATIONAL SPECTROSCOPY; MICROSOLVATED HYDRONIUM; HYDROGEN-BONDS; ZUNDEL; EIGEN;
D O I
10.1021/acs.jpca.7b01856
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Gas-phase H9O4+ has been considered an archetypal Eigen cation, H3O+(H2O)(3). Yet ab initio molecular dynamics (AIMD) suggested that its infrared spectrum is explained by a linear-chain Zundel isomer, alone or in a mixture with the Eigen cation. Recently, hole-burning experiments suggested a single isomer, with a second-order vibrational perturbation theory (VPT2) spectrum agreeing with the Eigen cation. To resolve this discrepancy, we have extended both calculations to more advanced DFT functionals, better basis sets, and dispersion correction. For Zundel-isomers, we find VPT2 anharmonic frequencies for four low-frequency modes involving the excess proton unreliable, including the 1750 cm(-1) band that is pivotal for differentiating between Zundel and Eigen isomers. Because the analogous bands of the H5O2+ cation show little effect of anharmonicity, we utilize the harmonic frequencies for these modes. With this caveat, both AIMD and VPT2 agree on the spectrum as originating from a Zundel isomer. VPT2 also shows that both isomers have the same spectrum in the high frequency region, so that the hole burning experiments should be extended to lower frequencies.
引用
收藏
页码:3056 / 3070
页数:15
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