Hydration of gaseous copper dications probed by IR action spectroscopy

被引:65
作者
O'Brien, Jeremy T. [1 ]
Williams, Evan R. [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
关键词
D O I
10.1021/jp7115643
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
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.
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页码:5893 / 5901
页数:9
相关论文
共 59 条
[51]   Photodissociation dynamics of hydrated Ni2+ clusters:: Ni2+(H2O)n (n=4-7) [J].
Thompson, CJ ;
Husband, J ;
Aguirre, F ;
Metz, RB .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (35) :8155-8159
[52]   The role of copper in neurodegenerative disease [J].
Waggoner, DJ ;
Bartnikas, TB ;
Gitlin, JD .
NEUROBIOLOGY OF DISEASE, 1999, 6 (04) :221-230
[53]   Solvation dynamics in Ni+(H2O)n clusters probed with infrared spectroscopy [J].
Walters, RS ;
Pillai, ED ;
Duncan, MA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (47) :16599-16610
[54]   Vibrational predissociation spectroscopy of Cs+(H2O)(1-5) [J].
Weinheimer, CJ ;
Lisy, JM .
JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (07) :2938-2941
[55]   Blackbody infrared radiative dissociation at low temperature:: hydration of X2+(H2O)n, for X = Mg, Ca [J].
Wong, RL ;
Paech, K ;
Williams, ER .
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY, 2004, 232 (01) :59-66
[56]   Dissociation of SO4 2-(H2O)n clusters, n=3-17 [J].
Wong, RL ;
Williams, ER .
JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (50) :10976-10983
[57]   VIBRATIONAL SPECTROSCOPY OF THE HYDRATED HYDRONIUM CLUSTER IONS H3O+.(H2O)N(N = 1, 2, 3) [J].
YEH, LI ;
OKUMURA, M ;
MYERS, JD ;
PRICE, JM ;
LEE, YT .
JOURNAL OF CHEMICAL PHYSICS, 1989, 91 (12) :7319-7330
[58]   A selective turn-on fluorescent sensor for imaging copper in living cells [J].
Zeng, L ;
Miller, EW ;
Pralle, A ;
Isacoff, EY ;
Chang, CJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (01) :10-11
[59]   Infrared spectroscopy of hydrated sulfate dianions [J].
Zhou, Jia ;
Santambrogio, Gabriele ;
Bruemmer, Mathias ;
Moore, David T. ;
Meijer, Gerard ;
Neumark, Daniel M. ;
Asmis, Knut R. .
JOURNAL OF CHEMICAL PHYSICS, 2006, 125 (11)