Počet záznamů: 1
Transforming Anion Instability into Stability: Contrasting Photoionization of Three Protonation Forms of the Phosphate Ion upon Moving into Water
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SYSNO ASEP 0385746 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Transforming Anion Instability into Stability: Contrasting Photoionization of Three Protonation Forms of the Phosphate Ion upon Moving into Water Tvůrce(i) Pluhařová, Eva (UOCHB-X) RID
Ončák, M. (CZ)
Seidel, R. (DE)
Schroeder, C. (US)
Schroeder, W. (US)
Winter, B. (DE)
Bradforth, S. E. (US)
Jungwirth, Pavel (UOCHB-X) RID, ORCID
Slavíček, P. (CZ)Celkový počet autorů 9 Zdroj.dok. Journal of Physical Chemistry B. - : American Chemical Society - ISSN 1520-6106
Roč. 116, č. 44 (2012), s. 13254-13264Poč.str. 11 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova multiply-charged anions ; ab-initio calculations ; aqueous-solution ; photoelectron-spectroscopy ; ionization energies ; emission-spectroscopy Vědní obor RIV CF - Fyzikální chemie a teoretická chemie CEP GAP208/10/1724 GA ČR - Grantová agentura ČR GA203/08/0114 GA ČR - Grantová agentura ČR CEZ AV0Z40550506 - UOCHB-X (2005-2011) UT WOS 000310768600012 DOI 10.1021/jp306348b Anotace We use photoelectron emission spectroscopy with vacuum microjet technique and quantum chemistry calculations to investigate electronic structure and stability of aqueous phosphate anions. On the basis of the measured photoelectron spectra of sodium phosphates at different pH, we report the lowest vertical ionization energies of monobasic (9.5 eV), dibasic (8.9 eV), and tribasic (8.4 eV) anions. Electron binding energies were in tandem modeled with ab initio methods, using a mixed dielectric solvation model together with up to 64 explicitly solvating water molecules. We demonstrate that two solvation layers of explicit water molecules are needed to obtain converged values of vertical ionization energies (VIEs) within this mixed solvation model, leading to very good agreement with experiment. We also show that the highly charged PO43- anion, which is electronically unstable in the gas phase, gains the electronic stability with about 16 water molecules, while only 2-3 water molecules are sufficient to stabilize the doubly charged phosphate anion. We also investigate the effect of ion pairing on the vertical ionization energy. In contrast to protonation (leading to a formation of covalent O-H bond), sodiation (leading to an anion center dot center dot center dot Na+ ion pair) has only a weak effect on the electron binding energy. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2013
Počet záznamů: 1