Reactions and Reaction Rate of Atmospheric SO2 and O3- (H2O)n Collisions via Molecular Dynamics Simulations

被引:17
作者
Bork, Nicolai [1 ,2 ]
Loukonen, Ville [1 ]
Vehkamaki, Hanna [1 ]
机构
[1] Univ Helsinki, Dept Phys, Div Atmospher Sci & Geophys, FIN-00014 Helsinki, Finland
[2] Univ Copenhagen, HC Orsted Inst, Dept Chem, DK-1168 Copenhagen, Denmark
基金
芬兰科学院;
关键词
AB-INITIO; SULFURIC-ACID; DENSITY; PARTICLE; NUCLEATION; OXIDATION; ENERGIES;
D O I
10.1021/jp311103z
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
We present an ab initio study of gaseous SO2 and O-3(-)(H2O)(n) collisions. Opposed to the usual approach to determine reaction rates via structural optimizations and transition state theory, we successfully approach this problem using ab initio molecular dynamics. We demonstrate the advantages of this approach, being the automatic and unbiased inclusion of dynamic and steric effects as well as the simultaneous assessment of all possible reactions. For this particular system, we find that only one reaction will be of atmospheric significance. Further, we identify the main geometrical parameters governing and limiting the observed reaction and suggest a new measure of the reaction rate being ca. 3/4 of the collision rate.
引用
收藏
页码:3143 / 3148
页数:6
相关论文
共 43 条
[1]   A simple and efficient CCSD(T)-F12 approximation [J].
Adler, Thomas B. ;
Knizia, Gerald ;
Werner, Hans-Joachim .
JOURNAL OF CHEMICAL PHYSICS, 2007, 127 (22)
[2]  
[Anonymous], 2018, Physical Chemistry
[3]   How many molecules make a solution? [J].
Bondybey, VE ;
Beyer, MK .
INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY, 2002, 21 (02) :277-306
[4]   Exploring the atmospheric chemistry of O2SO3- and assessing the maximum turnover number of ion-catalysed H2SO4 formation [J].
Bork, N. ;
Kurten, T. ;
Vehkamaki, H. .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2013, 13 (07) :3695-3703
[5]   Structures and reaction rates of the gaseous oxidation of SO2 by an O3-(H2O)0-5 cluster - a density functional theory investigation [J].
Bork, N. ;
Kurten, T. ;
Enghoff, M. B. ;
Pedersen, J. O. P. ;
Mikkelsen, K. V. ;
Svensmark, H. .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2012, 12 (08) :3639-3652
[6]   Ab initio studies of O2- (H2O)n and O3- (H2O)n anionic molecular clusters, n≤12 [J].
Bork, N. ;
Kurten, T. ;
Enghoff, M. B. ;
Pedersen, J. O. P. ;
Mikkelsen, K. V. ;
Svensmark, H. .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2011, 11 (14) :7133-7142
[7]   Thermodynamic and kinetic properties of hydrogen defect pairs in SrTiO3 from density functional theory [J].
Bork, Nicolai ;
Bonanos, Nikolaos ;
Rossmeisl, Jan ;
Vegge, Tejs .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2011, 13 (33) :15256-15263
[8]   CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].
BOYS, SF ;
BERNARDI, F .
MOLECULAR PHYSICS, 1970, 19 (04) :553-&
[9]   Assessment of Density Functional Theory in Predicting Structures and Free Energies of Reaction of Atmospheric Prenucleation Clusters [J].
Elm, Jonas ;
Bilde, Merete ;
Mikkelsen, Kurt V. .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2012, 8 (06) :2071-2077
[10]   An isotopic analysis of ionising radiation as a source of sulphuric acid [J].
Enghoff, M. B. ;
Bork, N. ;
Hattori, S. ;
Meusinger, C. ;
Nakagawa, M. ;
Pedersen, J. O. P. ;
Danielache, S. ;
Ueno, Y. ;
Johnson, M. S. ;
Yoshida, N. ;
Svensmark, H. .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2012, 12 (12) :5319-5327