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Statements

Subject Item
n2:RIV%2F60461373%3A22340%2F12%3A43894060%21RIV13-GA0-22340___
rdf:type
n17:Vysledek skos:Concept
dcterms:description
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. 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.
dcterms:title
Transforming Anion Instability into Stability: Contrasting Photoionization of Three Protonation Forms of the Phosphate Ion upon Moving into Water Transforming Anion Instability into Stability: Contrasting Photoionization of Three Protonation Forms of the Phosphate Ion upon Moving into Water
skos:prefLabel
Transforming Anion Instability into Stability: Contrasting Photoionization of Three Protonation Forms of the Phosphate Ion upon Moving into Water Transforming Anion Instability into Stability: Contrasting Photoionization of Three Protonation Forms of the Phosphate Ion upon Moving into Water
skos:notation
RIV/60461373:22340/12:43894060!RIV13-GA0-22340___
n17:predkladatel
n18:orjk%3A22340
n3:aktivita
n16:Z n16:P
n3:aktivity
P(GA203/08/0114), P(GAP208/10/1724), P(GAP208/11/0161), Z(AV0Z40550506)
n3:cisloPeriodika
44
n3:dodaniDat
n7:2013
n3:domaciTvurceVysledku
n15:1781073 n15:6431712
n3:druhVysledku
n4:J
n3:duvernostUdaju
n10:S
n3:entitaPredkladatele
n21:predkladatel
n3:idSjednocenehoVysledku
174905
n3:idVysledku
RIV/60461373:22340/12:43894060
n3:jazykVysledku
n19:eng
n3:klicovaSlova
HYDRATION; POTENTIAL FUNCTIONS; EMISSION-SPECTROSCOPY; LIQUID WATER; IONIZATION ENERGIES; GAS-PHASE; PHOTOELECTRON-SPECTROSCOPY; AQUEOUS-SOLUTION; AB-INITIO CALCULATIONS; MULTIPLY-CHARGED ANIONS
n3:klicoveSlovo
n8:IONIZATION%20ENERGIES n8:AB-INITIO%20CALCULATIONS n8:GAS-PHASE n8:HYDRATION n8:MULTIPLY-CHARGED%20ANIONS n8:POTENTIAL%20FUNCTIONS n8:LIQUID%20WATER n8:EMISSION-SPECTROSCOPY n8:AQUEOUS-SOLUTION n8:PHOTOELECTRON-SPECTROSCOPY
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[E23AEDDB7E09]
n3:nazevZdroje
JOURNAL OF PHYSICAL CHEMISTRY B
n3:obor
n11:CF
n3:pocetDomacichTvurcuVysledku
2
n3:pocetTvurcuVysledku
9
n3:projekt
n9:GAP208%2F11%2F0161 n9:GAP208%2F10%2F1724 n9:GA203%2F08%2F0114
n3:rokUplatneniVysledku
n7:2012
n3:svazekPeriodika
116
n3:tvurceVysledku
Ončák, Milan Schroeder, Christi Schroeder, William Winter, B. Slavíček, Petr Pluhařová, Eva Jungwirth, Pavel Seidel, Robert Bradforth, Stephan E
n3:wos
000310768600012
n3:zamer
n20:AV0Z40550506
s:issn
1520-6106
s:numberOfPages
11
n5:doi
10.1021/jp306348b
n14:organizacniJednotka
22340