Communication: Physical origins of ionization potential shifts in mixed carboxylic acids and water complexes
| Autor: | Wei Wu, Quanli Gu, Zhen Tang, Carl Trindle, Peifeng Su, Joseph L. Knee, Zhijun Yang |
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| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
010304 chemical physics Chemistry Formic acid Hydrogen bond Dimer Carboxylic acid Intermolecular force Binding energy General Physics and Astronomy 010402 general chemistry Photochemistry 01 natural sciences 0104 chemical sciences chemistry.chemical_compound Ionization 0103 physical sciences Organic chemistry Physical and Theoretical Chemistry Ionization energy |
| Zdroj: | The Journal of chemical physics. 145(5) |
| ISSN: | 1089-7690 |
| Popis: | The ionization potential (IP) of the aromatic alpha hydroxy carboxylic acid, 9-hydroxy-9-fluorene carboxylic acid (9HFCA), is shifted by complexation with hydrogen bonding ligands such as water and formic acid. Generalized Kohn-Sham energy decomposition analysis decomposes the intermolecular binding energies into a frozen energy term, polarization, correlation, and/or dispersion energy terms, as well as terms of geometric relaxation and zero point energy. We observe that in each dimer the attractive polarization always increases upon ionization, enhancing binding in the cation and shifting the IP toward the red. For 9HFCA—H2O, a substantial decrease of the repulsive frozen energy in cation further shifts the IP toward red. For 9HFCA—HCOOH, the increase of the frozen energy actually occurs in the cation and shifts the IP toward blue. Consistent with the experimental measurements, our analysis provides new, non-intuitive perspectives on multiple hydrogen bonds interactions in carboxylic acids and water complexes. |
| Databáze: | OpenAIRE |
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