MP4 Study of the Anharmonic Coupling of the Shared Proton Stretching Vibration of the Protonated Water Dimer in Equilibrium and Transition States
| Autor: | V. Pogorelov, Valdas Sablinskas, A. E. Malevich, E.N. Kozlovskaya, Lars G. M. Pettersson, I. Doroshenko, V. Balevicius, G. A. Pitsevich, E. Mahnach |
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| Rok vydání: | 2017 |
| Předmět: |
Coupling
Water dimer 010304 chemical physics Proton Chemistry Anharmonicity 010402 general chemistry 01 natural sciences Potential energy Transition state Symmetry (physics) 0104 chemical sciences Vibration 0103 physical sciences Physics::Chemical Physics Physical and Theoretical Chemistry Atomic physics |
| Zdroj: | The journal of physical chemistry. A. 121(10) |
| ISSN: | 1520-5215 |
| Popis: | The structure and harmonic and anharmonic IR spectra of the protonated water dimer (PWD) were calculated in C1, C2, and Cs symmetry at the MP4/acc-pVTZ level of theory. We found that structure and IR spectra are practically identical in C2 and C1 symmetry, demonstrating that an equilibrium C1 configuration of the PWD is not realized. Anharmonic coupling of the shared proton stretching vibration with all other modes in the PWD in C2 and Cs symmetry was the focus of this investigation. For this purpose, 28 two-dimensional potential energy surfaces (2D PES) were built at the MP4/acc-pVTZ level of theory and the corresponding vibrational Schrodinger equations were solved using the DVR method. Differences in the coupling of the investigated mode with other modes in the C2 and Cs configurations, along with some factors that determine the red- or blue-shift of the stretching vibration frequency, were analyzed. We obtained a rather reasonable value of the stretching frequency of the bridging proton (1058.4 cm–1) ... |
| Databáze: | OpenAIRE |
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