TY - JOUR
T1 - Analysis of gas phase proton transfer using density functional theory. The H2O · · · HX (X = F, Cl and OH) system
AU - Pérez, Patricia
AU - Contreras, Renato
N1 - Funding Information:
The work was supported by FONDECYT under contract 2960011. PP is a Conicyt Graduate Program Fellow.
PY - 1996/6
Y1 - 1996/6
N2 - The gas phase proton transfer for the system H2O · · · HX (X = F, Cl and OH) is analyzed in detail using density functional theory. The process is decomposed into H-bonding, ion pairing and dissociation contributions by means of a thermodynamic cycle that uses a water molecule as a proton relay agent. For each step, the energy variations are partitioned into its electrostatic and non-electrostatic contributions. The analysis shows that the principle of maximum hardness is fulfilled for all three processes considered in the proton transfer reaction. The present approach surprisingly yields accurate values for the proton affinity of the F-, Cl- and OH- ions.
AB - The gas phase proton transfer for the system H2O · · · HX (X = F, Cl and OH) is analyzed in detail using density functional theory. The process is decomposed into H-bonding, ion pairing and dissociation contributions by means of a thermodynamic cycle that uses a water molecule as a proton relay agent. For each step, the energy variations are partitioned into its electrostatic and non-electrostatic contributions. The analysis shows that the principle of maximum hardness is fulfilled for all three processes considered in the proton transfer reaction. The present approach surprisingly yields accurate values for the proton affinity of the F-, Cl- and OH- ions.
UR - http://www.scopus.com/inward/record.url?scp=0030167076&partnerID=8YFLogxK
U2 - 10.1016/0009-2614(96)00437-X
DO - 10.1016/0009-2614(96)00437-X
M3 - Article
AN - SCOPUS:0030167076
VL - 256
SP - 15
EP - 20
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 1-2
ER -