Probing the Low-Barrier Hydrogen Bond in Hydrogen Maleate in the Gas Phase: A Photoelectron Spectroscopy and ab Initio Study
The strength of the low-barrier hydrogen bond in hydrogen maleate in the gas phase was investigated by low-temperature photoelectron spectroscopy and ab initio calculations. Photoelectron spectra of maleic and fumaric acid monoanions (cis-/trans-HO2CCHdCHCO2 -) were obtained at low temperatures and at 193 nm photon energy. Vibrational structure was observed for trans-HO2CCHdCHCO2 - due to the OCO bending modes; however, cis-HO2CCHdCHCO2 - yielded a broad and featureless spectrum. The electron binding energy of cis-HO2CCHdCHCO2 - is about 1 eV blue-shifted relative to trans-HO2CCHdCHCO2 - due to the formation of intramolecular hydrogen bond in the cis-isomer. Theoretical calculations (CCSD(T)/ aug-cc-pVTZ and B3LYP/aug-cc-pVTZ) were carried out to estimate the strength of the intramolecular hydrogen bond in cis-HO2CCHdCHCO2 -. Combining experimental and theoretical calculations yields an estimate of 21.5 ( 2.0 kcal/mol for the intramolecular hydrogen bond strength in hydrogen maleate.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 876996
- Report Number(s):
- PNNL-SA-47874; JPCAFH; 1391a; 1391; KC0301020; TRN: US200608%%359
- Journal Information:
- Journal of Physical Chemistry A, 109(47):10633-10637, Vol. 109, Issue 47; ISSN 1089-5639
- Country of Publication:
- United States
- Language:
- English
Similar Records
Comparison of Some Representative Density Functional Theory and Wave Function Theory Methods for the Studies of Amino Acids
The Heats of Formation of Diazene, Hydrazine, N₂H₃ ⁺, N₂H₅ +, N₂H, and N₂H₃ and the Methyl Derivatives CH₃NNH, CH₃NNCH₃, and CH₃HNNHCH₃.