Electronic Structures of Formic Acid (HCOOH) and Formate (HCOO-) in Aqueous Solutions

被引：38

作者：

Brown, Matthew A. ^{[1
]}

Vila, Fernando ^{[2
]}

Sterrer, Martin ^{[3
]}

Thuermer, Stephan ^{[4
,5
]}

Winter, Bernd ^{[4
,5
]}

Ammann, Markus ^{[6
]}

Rehr, John J. ^{[2
]}

van Bokhoven, Jeroen A. ^{[1
,7
]}

机构：

[1] ETH, Inst Chem & Bioengn, CH-8093 Zurich, Switzerland

[2] Univ Washington, Dept Phys, Seattle, WA 98195 USA

[3] Max Planck Gesell, Fritz Haber Inst, Dept Chem Phys, D-14195 Berlin, Germany

[4] Helmholtz Zentrum Berlin Mat & Energie, D-12489 Berlin, Germany

[5] BESSY, D-12489 Berlin, Germany

[6] Paul Scherrer Inst, Lab Radiochem & Environm Chem, CH-5232 Villigen, Switzerland

[7] Paul Scherrer Inst, Swiss Light Source, CH-5232 Villigen, Switzerland

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2012年 / 3卷 / 13期

关键词：

X-RAY-ABSORPTION; CARBOXYLIC-ACIDS; LIQUID/VAPOR INTERFACE; CAR-PARRINELLO; BASIS-SETS; IN-SITU; SPECTROSCOPY; DECOMPOSITION; APPROXIMATION; PHOTOEMISSION;

D O I：

10.1021/jz300510r

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：

The electronic structures of formic acid (HCOOH) and formate (HCOO-) have been determined in aqueous solutions over a pH range of 1.88-8.87 using a combination of X-ray photoelectron spectroscopy (XPS), partial electron-yield X-ray absorption spectroscopy (PEY XAS), and density functional theory (DFT). The carbon Is XPS measurements reveal a binding energy shift of -1.3 eV for deprotonated HCOO compared with neutral HCOOH. Such distinction between neutral HCOOH and deprotonated HCOO- cannot be made based solely on the respective carbon K-edge PEY XA spectra. Independent of pH, the C1s -> pi* state excitations occur at 288.0 eV and may lead to the incorrect conclusion that the energy levels of the pi* state are the same for both species. The DFT calculations are consistent with the experimental observations and show a shift to higher energy for both the occupied C1s (lower binding energy) and unoccupied pi* orbitals of deprotonated HCOO- compared to neutral HCOOH in aqueous solutions.

引用

页码：1754 / 1759

页数：6

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