Electric field gradients in Hg compounds: Molecular orbital (MO) analysis and comparison of 4-component and 2-component (ZORA) methods

被引:14
作者
Arcisauskaite, Vaida [1 ]
Knecht, Stefan [2 ]
Sauer, Stephan P. A. [1 ]
Hemmingsen, Lars [1 ]
机构
[1] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen O, Denmark
[2] Univ So Denmark, Dept Phys Chem & Pharm, DK-5230 Odense M, Denmark
关键词
NUCLEAR-QUADRUPOLE INTERACTION; DENSITY-FUNCTIONAL THEORY; GAUSSIAN-BASIS SETS; ZETA BASIS-SETS; AB-INITIO; COUPLING-CONSTANTS; HG(II) COORDINATION; CADMIUM COMPLEXES; B3LYP CALCULATION; HARTREE-FOCK;
D O I
10.1039/c2cp42291c
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
We examine the performance of Density Functional Theory (DFT) approaches based on the Zeroth-Order Regular Approximation (ZORA) Hamiltonian (with and without inclusion of spin-orbit coupling) for predictions of electric field gradients (EFGs) at the heavy atom Hg nucleus. This is achieved by comparing with benchmark DFT and CCSD-T data (Arcisauskaite et al., Phys. Chem. Chem. Phys., 2012, 14, 2651-2657) obtained from 4-component Dirac-Coulomb Hamiltonian calculations. The investigated set of molecules comprises linear HgL2 (L = Cl, Br, I, CH3) and bent HgCl2 mercury compounds as well as the trigonal planar [HgCl3](-) system. In 4-component calculations we used the dyall. cv3z basis set for Hg, Br, I and the cc-pCVTZ basis set for H, C, Cl, whereas in ZORA calculations we used the QZ4P basis set for all the atoms. ZORA-4 reproduces the fully relativistic 4-component DFT reference values within 6% for all studied Hg compounds and employed functionals (BH&H, BP86, PBE0), whereas scalar relativistic (SR)-ZORA-4 results show deviations of up to 15%. Compared to our 4-component CCSD-T benchmark the BH&H functional performs best at both 4-component and ZORA levels. We furthermore observe that changes in the largest component of the diagonalised EFG tensor, V-zz, of linear HgCl2 show a slightly stronger dependence than the r(-3) scaling upon bond length r(Hg-Cl) alterations. The 4-component/BH&H V-zz value of -9.26 a. u. for a bent HgCl2 (+Cl-Hg-Cl = 120 degrees) is close to -9.60 a. u. obtained for the linear HgCl2 structure. Thus a point charge model for EFG calculations completely fails in this case. By means of a projection analysis of molecular orbital (MO) contributions to V-zz in terms of the atomic constituents, we conclude that this is due to the increased importance of the Hg 5d orbitals upon bending HgCl2 compared to the linear HgCl2 structure. Changing ligand leads to only minor changes in V-zz (from -9.60 a. u. (HgCl2) to -8.85 a. u. (HgI2) at the 4-component/BH&H level). This appears to be due to cancellation of contributions with opposite signs to V-zz arising from: (i) increasing electron donation from occupied ligand orbitals to the formally empty Hg 6p orbitals and (ii) an increasing bond length and a decreasing negative charge on the ligand along the series.
引用
收藏
页码:16070 / 16079
页数:10
相关论文
共 82 条
[1]   Toward reliable density functional methods without adjustable parameters: The PBE0 model [J].
Adamo, C ;
Barone, V .
JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) :6158-6170
[2]  
AKISHIN PA, 1959, ZH FIZ KHIM+, V33, P20
[3]  
[Anonymous], 2011, DIRAC RELATIVISTIC A
[4]  
[Anonymous], ADF2010 SCM THEOR CH
[5]   Density functional calculation of the electric field gradient in cadmium complexes: Comparison with Hartree-Fock, second-order Moller-Plesset, and experimental results [J].
Antony, J ;
Hansen, B ;
Hemmingsen, L ;
Bauer, R .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (25) :6047-6055
[6]   Electric Field Gradients Calculated from Two-Component Hybrid Density Functional Theory Including Spin-Orbit Coupling [J].
Aquino, Fredy ;
Govind, Niranjan ;
Autschbach, Jochen .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2010, 6 (09) :2669-2686
[7]   Fully relativistic coupled cluster and DFT study of electric field gradients at Hg in 199Hg compounds [J].
Arcisauskaite, Vaida ;
Knecht, Stefan ;
Sauer, Stephan P. A. ;
Hemmingsen, Lars .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2012, 14 (08) :2651-2657
[8]   Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: A comparison of three relativistic computational methods [J].
Arcisauskaite, Vaida ;
Melo, Juan I. ;
Hemmingsen, Lars ;
Sauer, Stephan P. A. .
JOURNAL OF CHEMICAL PHYSICS, 2011, 135 (04)
[9]   Analysis of Electric Field Gradient Tensors at Quadrupolar Nuclei in Common Structural Motifs [J].
Autschbach, Jochen ;
Zheng, Shaohui ;
Schurko, Robert W. .
CONCEPTS IN MAGNETIC RESONANCE PART A, 2010, 36A (02) :84-126
[10]   B3LYP calculation of deuterium quadrupole coupling constants in molecules [J].
Bailey, WC .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1998, 190 (02) :318-323