Performance of density functional theory methods for the treatment of metal-ligand dications

被引:42
作者
Alcamí, M [1 ]
González, AI [1 ]
Mó, O [1 ]
Yáñez, M [1 ]
机构
[1] Univ Autonoma Madrid, Dept Quim, E-28049 Madrid, Spain
关键词
D O I
10.1016/S0009-2614(99)00513-8
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
The performance of different density functional theory approaches for the treatment of MgX2+ (X = H2O, CH2O, CH3OH, NH3, CH2NH, HCN, CH3NH2, NH2OH) and CaX2+ (X = H2O, NH3) metal-ligand dications was investigated. The DFT results were compared with high-level ab initio calculations carried out at the QCISD(T)/6-311 + G(3df,2p)//QCISD/6-311G* and CCSD(T)/6-311 + G(3df,2p)//QCISD/6-311G* levels of theory. In general, the hybrid DFT methods yield X-Mg2+ bond distances which are too short compared with the QCISD/6-311G* optimized ones. En contrast, non-hybrid DFT approaches, such as BLYP or G96LYP, yield longer X-Mg2+ bond distances, which are in better agreement with the QCISD ones. The DFT methods investigated, with the exception of the G96LYP approach, yield Mg2+ binding energies 2.0 to 6.0 kcal/mof larger than those obtained using high-level ab initio techniques. These differences are smaller when the metal dication is Ca2+. (C) 1999 Elsevier Science B.V. All rights reserved.
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页码:244 / 252
页数:9
相关论文
共 35 条
[1]   Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters:: The mPW and mPW1PW models [J].
Adamo, C ;
Barone, V .
JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (02) :664-675
[2]  
AKESSON R, 1992, J PHYS CHEM-US, V96, P10773, DOI 10.1021/j100205a034
[3]   A THEORETICAL-STUDY OF THE POSITIVE AND DIPOSITIVE IONS OF M(NH3)N AND M(H2O)N FOR M=MG, CA, OR SR [J].
BAUSCHLICHER, CW ;
SODUPE, M ;
PARTRIDGE, H .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (06) :4453-4463
[4]   THE C-H DISSOCIATION-ENERGY OF C2H6 [J].
BAUSCHLICHER, CW ;
PARTRIDGE, H .
CHEMICAL PHYSICS LETTERS, 1995, 239 (4-6) :246-251
[5]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[6]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[7]   Extension of Gaussian-2 (G2) theory to molecules containing third-row atoms K and Ca [J].
Blaudeau, JP ;
McGrath, MP ;
Curtiss, LA ;
Radom, L .
JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (13) :5016-5021
[8]   HYDRATION OF ZINC IONS - A COMPARISON WITH MAGNESIUM AND BERYLLIUM IONS [J].
BOCK, CW ;
KATZ, AK ;
GLUSKER, JP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (13) :3754-3763
[9]   Interaction of DNA base pairs with various metal cations (Mg2+, Ca2+, Sr2+, Ba2+, Cu+, Ag+, Au+, Zn2+, Cd2+, and Hg2+): Nonempirical ab initio calculations on structures, energies, and nonadditivity of the interaction [J].
Burda, JV ;
Sponer, J ;
Leszczynski, J ;
Hobza, P .
JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (46) :9670-9677
[10]  
Burke K., 1998, ELECT DENSITY FUNCTI