Theoretical description of copper Cu(I)/Cu(II) complexes in mixed ammine-aqua environment. DFT and ab initio quantum chemical study

被引:64
作者
Pavelka, M [1 ]
Burda, JV [1 ]
机构
[1] Charles Univ Prague, Fac Math & Phys, Dept Chem Phys & Opt, CR-12116 Prague, Czech Republic
关键词
DFT calculations; copper complexes;
D O I
10.1016/j.chemphys.2004.11.034
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
This work is devoted to investigate the interactions of the Cu(l)/Cu(II) cation with variable ammonia-water ligand field by the quantum chemical approach. For that purpose, the optimization of the [Cu(NH3)(m)(H2O)(n)](2+/+) complexes (where it varies from 0 to 4 or 6 and in + it = 4 or 6) has been performed at the DFT/6-31+G(d) level of theory in conjunction with the B3PW91 hybrid functional. Based on the results of the single-point B3LYP/6-311 ++G(2df,2pd) calculations, the stabilization energies were determined. The two-coordinated copper(l) complexes appeared to be the most stable compounds with the remaining water or ammonia molecules in the second solvation shell. In the case of the Cu(II) systems, four-coordinated complexes were found to be the most stable. In order to examine and explain bonding characteristics, Morokuma interaction energy decomposition (for selected Cut complexes) and Natural Population Analysis for all systems were performed. It was found that the most stable structures correlate with the highest donation effects. Therefore, more polarizable ammonia molecules exhibit higher donation than water and thus make stronger bonds to copper. This can be demonstrated by the fact that the NH3 molecule always tries to occupy the first solvation shell in mixed ammine-aqua complexes. (c) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码:193 / 204
页数:12
相关论文
共 68 条
[11]   ABINITIO COPPER WATER INTERACTION POTENTIAL FOR THE SIMULATION OF AQUEOUS-SOLUTIONS [J].
CORDEIRO, MNDS ;
GOMES, JANF .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 1993, 14 (06) :629-638
[12]   Structures and binding enthalpies of M+ (H2O)n clusters, M=Cu, Ag, Au [J].
Feller, D ;
Glendening, ED ;
de Jong, WA .
JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (03) :1475-1491
[13]  
FELLER D, 1999, J CHEM PHYS, V110
[14]   Charge-transfer dynamics in plastocyanin, a blue copper protein, from resonance Raman intensities [J].
Fraga, E ;
Webb, MA ;
Loppnow, GR .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (08) :3278-3287
[15]  
FRISCH GW, 2001, GAUSSIAN 98 REVISION
[16]   MODE OF COORDINATION AND STABILITY OF CU(II) AND ZN(II) COMPLEXES WITH ADENOSINE, DEOXYADENOSINE, CYTIDINE AND DEOXYCYTIDINE [J].
GASOWSKA, A ;
LOMOZIK, L .
MONATSHEFTE FUR CHEMIE, 1995, 126 (01) :13-22
[17]   Copper coordination in blue proteins [J].
Gray, HB ;
Malmström, BG ;
Williams, RJP .
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY, 2000, 5 (05) :551-559
[18]   Modeling copper(I) complexes: SIBFA molecular mechanics versus ab initio energetics and geometrical arrangements [J].
Gresh, N ;
Policar, C ;
Giessner-Prettre, C .
JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (23) :5660-5670
[19]   Study of Ca2+, Mn2+ and Cu2+ binding to DNA in solution by means of IR spectroscopy [J].
Hackl, EV ;
Kornilova, SV ;
Kapinos, LE ;
Andrushchenko, VV ;
Galkin, VL ;
Grigoriev, DN ;
Blagoi, YP .
JOURNAL OF MOLECULAR STRUCTURE, 1997, 408 :229-232
[20]  
HAEFFNER F, 1997, CHEM PHYS LETT, V397, P39