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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Hydration of gaseous copper dications probed by IR action spectroscopy
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Hydration of gaseous copper dications probed by IR action spectroscopy

机译：红外光谱法探测气态铜的水合

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摘要

Clusters of Cu2+(H2O)(n), n = 6-12, formed by electrospray ionization, are investigated using infrared photodissociation spectroscopy, blackbody infrared radiative dissociation (BIRD), and density functional theory of select clusters. At 298 K, the BIRD rate constants increase with increasing cluster size for n >= 8, but the trend reverses for the smaller clusters where Cu2+ (H2O)(6) is less stable than Cu2+(H2O)(8). This trend in stability is consistent with a change in fragmentation pathway from loss of a water molecule for clusters with n >= 9 to loss of hydrated protonated water clusters and the formation of the corresponding singly charged hydrated metal hydroxide for n <= 7. The lowest-energy structures of Cu2+(H2O)(n), n = 6-8 and 10, identified at the B3LYP/LACV3P**++ levelof theory, all have coordination numbers (CN) of 4, although structures with a CN = 5 are within about 10 kJ/mol for all clusters except Cu2+(H2O)(8). IR action spectra indicate the presence of hydrogen bonding for all clusters, and results for Cu2+(H2O)(n), n = 6-8, are consistent with a CN = 4, although minor contributions from structures with higher CN cannot be ruled out. Bands in the action spectra of Cu2+(H2O)(n), n = 10-12, show the presence of water molecules that accept two hydrogen bonds and donate one hydrogen bond as well as single hydrogen bond acceptors clearly indicating the onset for formation of a third solvent shell at a relatively small cluster size.
机译：使用红外光解离光谱，黑体红外辐射解离（BIRD）和选择簇的密度泛函理论研究了电喷雾电离形成的Cu2 +（H2O）（n）簇，n = 6-12。在298 K时，当n> = 8时，BIRD速率常数随簇大小的增加而增加，但对于Cu2 +（H2O）（6）较Cu2 +（H2O）（8）不稳定的较小簇，趋势相反。这种稳定性趋势与从n> = 9的团簇的水分子损失到水合的质子化水团簇的损失以及n <= 7的相应的单电荷水合金属氢氧化物的裂解途径的改变相一致。在B3LYP / LACV3P ** ++理论水平上确定的Cu2 +（H2O）（n）的最低能级结构，n = 6-8和10，尽管它们的CN =除Cu2 +（H2O）（8）外，所有簇的5均在约10 kJ / mol之内。红外作用谱表明所有簇均存在氢键，Cu2 +（H2O）（n）的结果（n = 6-8）与CN = 4一致，尽管不能排除具有较高CN的结构的微小贡献。 Cu2 +（H2O）（n）的作用谱带中的n = 10-12，表明存在接受两个氢键并提供一个氢键的水分子以及单个氢键受体，清楚地表明了形成第三溶剂壳的簇尺寸相对较小。

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