Computational studies at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels are performed to explore the changes in reaction barrier height for the gas phase hydrolysis of SO(3) to form H(2)SO(4) in the presence of a single formic acid (FA) molecule. For comparison, we have also performed calculations for the reference reaction involving water assisted hydrolysis of SO(3) at the same level. Our results show that the FA assisted hydrolysis of SO(3) to form H(2)SO(4) is effectively a barrierless process. The barrier heights for the isomerization of the SO(3)···H(2)O···FA prereactive collision complex, which is the rate limiting step in the FA assisted hydrolysis, are found to be respectively 0.59 and 0.08 kcal/mol at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels. This is substantially lower than the ~7 kcal/mol barrier for the corresponding step in the hydrolysis of SO(3) by two water molecules--which is currently the accepted mechanism for atmospheric sulfuric acid production. Simple kinetic analysis of the relative rates suggests that the reduction in barrier height facilitated by FA, combined with the greater stability of the prereactive SO(3)···H(2)O···FA collision complex compared to SO(3)···H(2)O···H(2)O and the rather plentiful atmospheric abundance of FA, makes the formic acid mediated hydrolysis reaction a potentially important pathway for atmospheric sulfuric acid production.

We find that formic acid (FA) is very effective at facilitating diol formation through its ability to reduce the barrier for the formaldehyde (HCHO) hydrolysis reaction. The rate limiting step in the mechanism involves the isomerization of a prereactive collision complex formed through either the HCHO···H2O + FA and/or HCHO + FA···H2O pathways. The present study finds that the effective barrier height, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state (TS) and the HCHO···H2O + FA and HCHO + FA···H2O starting reagents, are respectively only ∼1 and ∼4 kcal/mol. These barriers are substantially lower than the ∼17 kcal/mol barrier associated with the corresponding step in the hydrolysis of HCHO catalyzed by a single water molecule (HCHO + H2O + H2O). The significantly lower barrier heights for the formic acid catalyzed pathway reveal a new important role that organic acids play in the gas phase hydrolysis of atmospheric carbonyl compounds.

We show that hydrothermal treatment of citric acid produces methylenesuccinic acid, which gives rise to hydrogen-bonded nano-assemblies with CND-like properties.

The hydrolysis of glyoxal involving one to three water molecules and also in the presence of a water molecule and formic acid has been investigated. Our results show that glyoxal-diol is the major product of the hydrolysis and that formic acid, through its ability to facilitate intermolecular hydrogen atom transfer, is considerably more efficient than water as a catalyst in the hydrolysis process. Additionally, once the glyoxal-diol is formed, the barrier for further hydrolysis to form the glyoxal-tetrol is effectively reduced to zero in the presence of a single water and formic acid molecule. There are two important implications arising from these findings. First, the results suggest that under the catalytic influence of formic acid, glyoxal hydrolysis can impact the growth of atmospheric aerosols. As a result of enhanced hydrogen bonding, mediated through their polar OH functional groups, the diol and tetrol products are expected to have significantly lower vapor pressure than the parent glyoxal molecule; hence they can more readily partition into the particle phase and contribute to the growth of secondary organic aerosols. In addition, our findings provide insight into how glyoxal-diol and glyoxal-tetrol might be formed under atmospheric conditions associated with water-restricted environments and strongly suggest that the formation of these precursors for secondary organic aerosol growth is not likely restricted solely to the bulk aqueous phase as is currently assumed.

Formic acid catalyzed tautomeric conversion of formamide to formamidic acid has been investigated by use of ab initio and density functional theoretical calculations. In a 1:1 dimeric complex between formamide and formic acid, the tautomeric conversion occurs via double-hydrogen transfer within an eight-member hydrogen-bonded cyclic network. The results predict that the energy barrier of the catalytic process is reduced by more than a factor of 4 compared to that in the isolated formamide molecule in the gas phase, and the tautomerization in the 1:1 complex is several kcal/mol less endothermic than that of the isolated molecule. The potential energy surface corresponding to this double hydrogen transfer process indicates that a concerted transfer of both the hydrogen atoms along the hydrogen bond directions is energetically favorable, and no minimum for an ionic intermediate, which may arise for stepwise transfer, was predicted. The unique configuration of the transition state has been identified by starting the reaction from both the tautomeric forms, and the transition state was subjected to IRC calculation.

A 1:1 hydrogen-bonded complex between 2-pyridone and formic acid has been characterized using laser-induced-fluorescence excitation and dispersed fluorescence spectroscopy in a supersonic jet expansion. Under the same expansion condition, the fluorescence signal of the tautomeric form of the complex (2-hydroxypyridine...formic acid) is absent, although both the bare tautomeric molecules exhibit well-resolved laser-induced-fluorescence spectra. Quantum chemistry calculation at the DFT/B3LYP/6-311++G** level predicts that in the ground electronic state the activation barrier for tautomerization from hydroxy to keto form in bare molecules is very large (approximately 34 kcal/mol). However, the process turns out to be nearly barrierless when assisted by formic acid, and double proton transfer occurs via a concerted mechanism.

In this article, we present high level ab initio calculations investigating the energetics of a new autocatalytic decomposition mechanism for carbonic acid (H2CO3) in the vapor phase. The calculation have been performed at the MP2 level of theory in conjunction with aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(3df,3pd) basis sets as well as at the CCSD(T)/aug-cc-pVTZ level. The present study suggests that this new decomposition mechanism is effectively a near-barrierless process at room temperature and makes vapor phase of H2CO3 unstable even in the absence of water molecules. Our calculation at the MP2/aug-cc-pVTZ level predicts that the effective barrier, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, is nearly zero for the autocatalytic decomposition mechanism. The results at the CCSD(T)/aug-cc-pVTZ level of calculations suggest that the effective barrier, as defined above, is sensitive to some extent to the levels of calculations used, nevertheless, we find that the effective barrier height predicted at the CCSD(T)/aug-cc-pVTZ level is very small or in other words the autocatalytic decomposition mechanism presented in this work is a near-barrierless process as mentioned above. Thus, we suggest that this new autocatalytic decomposition mechanism has to be considered as the primary mechanism for the decomposition of carbonic acid, especially at its source, where the vapor phase concentration of H2CO3 molecules reaches its highest levels.

Carbonic acid decomposition of potential atmospheric significance.