Amines are likely to enhance neutral and ion-induced sulfuric acid-water nucleation in the atmosphere more effectively than ammonia

We have studied the structure and formation thermodynamics of dimer clusters containing H 2 SO 4 or HSO 4 − together with ammonia and seven different amines possibly present in the atmosphere, using the high-level ab initio methods RI-MP2 and RI-CC2. As expected from e.g. proton affinity data, the binding of all studied amine-H 2 SO 4 complexes is significantly stronger than that of NH 3 •H 2 SO 4 , while most amine-HSO 4 − complexes are only somewhat more strongly bound than NH 3 •HSO 4 − . Further calculations on larger cluster structures containing dimethylamine or ammonia together with two H 2 SO 4 molecules or one H 2 SO 4 molecule and one HSO 4 − ion demonstrate that amines, unlike ammonia, significantly assist the growth of not only neutral but also ionic clusters along the H 2 SO 4 co-ordinate. A sensitivity analysis indicates that the difference in complexation free energies for amine- and ammonia-containing clusters is large enough to overcome the mass-balance effect caused by the fact that the concentration of amines in the atmosphere is probably 2 or 3 orders of magnitude lower than that of ammonia. This implies that amines might be more important than ammonia in enhancing neutral and especially ion-induced sulfuric acid-water nucleation in the atmosphere.

[1]  L. Pirjola,et al.  Stable sulphate clusters as a source of new atmospheric particles , 2000, Nature.

[2]  I. Riipinen,et al.  Toward Direct Measurement of Atmospheric Nucleation , 2007, Science.

[3]  Paul J. Crutzen,et al.  Emission of aliphatic amines from animal husbandry and their reactions: Potential source of N2O and HCN , 1995 .

[4]  Hans W. Horn,et al.  ELECTRONIC STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS: THE PROGRAM SYSTEM TURBOMOLE , 1989 .

[5]  D. R. Hanson,et al.  Laboratory studies of particle nucleation: Initial results for H2SO4, H2O, and NH3 vapors , 1999 .

[6]  M. Kulmala,et al.  The significant role of ammonia in atmospheric nanoclusters , 2006 .

[7]  K. Hämeri,et al.  Chemical composition of aerosol during particle formation events in boreal forest , 2001 .

[8]  Robert G. Flocchini,et al.  Characterization and quantification of odorous and non-odorous volatile organic compounds near a commercial dairy in California , 2003 .

[9]  Angela K. Wilson,et al.  Gaussian basis sets for use in correlated molecular calculations. X. The atoms aluminum through argon revisited , 2001 .

[10]  Pasi Aalto,et al.  Aerosol formation: Atmospheric particles from organic vapours , 2002, Nature.

[11]  Pasi Aalto,et al.  A new feedback mechanism linking forests, aerosols, and climate , 2003 .

[12]  Holger Patzelt,et al.  RI-MP2: optimized auxiliary basis sets and demonstration of efficiency , 1998 .

[13]  M. Kulmala,et al.  Quantum chemical studies of hydrate formation of h 2 so 4 and hso 4 – , 2007 .

[14]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1997 .

[15]  M. Kulmala,et al.  Effect of ammonium bisulphate formation on atmospheric water-sulphuric acid-ammonia nucleation , 2005 .

[16]  S. Haapanala,et al.  Hot-air Balloon Measurements of Vertical Variation of Boundary Layer New Particle Formation , 2007 .

[17]  K. Laasonen,et al.  A density functional study on water-sulfuric acid-ammonia clusters and implications for atmospheric cluster formation , 2007 .

[18]  M. Kulmala,et al.  Estimating the NH 3 :H 2 SO 4 ratio of nucleating clusters in atmospheric conditions using quantum chemical methods , 2007 .

[19]  F. Weigend,et al.  RI-MP2: first derivatives and global consistency , 1997 .

[20]  F. Weigend,et al.  Efficient use of the correlation consistent basis sets in resolution of the identity MP2 calculations , 2002 .

[21]  Marco Häser,et al.  Improvements on the direct SCF method , 1989 .

[22]  J. Seinfeld,et al.  Ternary nucleation of H2SO4, NH3, and H2O in the atmosphere , 1999 .

[23]  M. Kulmala,et al.  The role of ammonia in sulfuric acid ion induced nucleation , 2008 .

[24]  K. Sellegri,et al.  Measurements of organic gases during aerosol formation events in the boreal forest atmosphere during QUEST , 2004 .

[25]  E. P. Hunter,et al.  Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update , 1998 .

[26]  David Feller,et al.  Application of systematic sequences of wave functions to the water dimer , 1992 .

[27]  K. Froyd,et al.  Atmospheric ion‐induced nucleation of sulfuric acid and water , 2004 .

[28]  Alexey B. Nadykto,et al.  Strong hydrogen bonding between atmospheric nucleation precursors and common organics , 2007 .

[29]  John H. Seinfeld,et al.  Secondary aerosol formation from atmospheric reactions of aliphatic amines , 2007 .

[30]  K. Prather,et al.  Formation of aerosol particles from reactions of secondary and tertiary alkylamines: characterization by aerosol time-of-flight mass spectrometry. , 2001, Environmental science & technology.

[31]  Hanna Vehkamäki,et al.  Formation and growth rates of ultrafine atmospheric particles: a review of observations , 2004 .

[32]  Poul Jørgensen,et al.  The second-order approximate coupled cluster singles and doubles model CC2 , 1995 .

[33]  K. Laasonen,et al.  Significance of ammonia in growth of atmospheric nanoclusters. , 2007, The journal of physical chemistry. A.

[34]  G. Mann,et al.  The contribution of boundary layer nucleation events to total particle concentrations on regional and global scales , 2006 .