Calculation of bromine nuclear quadrupole coupling constants in gaseous state molecules

被引：14

作者：

Bailey, WC ^{[1
]}

Gonzalez, FM ^{[1
]}

机构：

[1] Kean Univ, Dept Chem & Phys, Union, NJ 07083 USA

来源：

JOURNAL OF MOLECULAR STRUCTURE | 2003年 / 651卷

关键词：

Br-79; Br-81; nuclear quadrupole coupling constants; density functional theory;

D O I：

10.1016/S0022-2860(02)00671-3

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：

Several DFT and hybrid HF/DFT methods in conjunction with Pople (6-311G) and Ahlrichs (TZV) bases have been investigated for the calculation of Br-79 and Br-81 nuclear quadrupole coupling constants (nqccs) in gaseous state molecules. The molecules are HBr, BrF, BrCl, Br-2, BrCN, BrBO, HCCBr, CH3Br, CH2Br2, CF3Br, CH2CHBr, and CH3CH2Br. Assessment of the various models was made by linear regression analysis of calculated electric fields versus experimental nqccs. The best results are obtained with the B1LYP, B3LYP, and LG1LYP hybrid methods combined with Ahlrichs' TZV bases plus polarization. With the B1LYP/TZV(3df, 3p) model, for example, the residual standard deviation for Br-79 is 1.7 MHz (0.42%), and for Br-81, 1.5 MHz (0.42%). The effective nuclear electric quadrupole moments derived from the slopes of the regression lines are, respectively, 330.4 and 276.0 mb. This B1LYP model is applied to calculation of the Br-79 nqccs in SiF3Br and SiH3Br for the purpose of investigation of the SiBr bond lengths. (C) 2003 Elsevier Science B.V. All rights reserved.

引用

页码：689 / 695

页数：7

共 43 条

[1]

Adamo C, 1998, J COMPUT CHEM, V19, P418, DOI 10.1002/(SICI)1096-987X(199803)19:4<418::AID-JCC4>3.0.CO

[2]

2-V

[3] Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters:: The mPW and mPW1PW models [J].