Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
J Chem Phys. 2011 Oct 7;135(13):134114. doi: 10.1063/1.3645182.
We present the first gauge-origin independent formulation of Jones birefringence at the Hartree-Fock level of theory. Gauge-origin independence is achieved through the use of London atomic orbitals. The implementation is based on a recently proposed atomic orbital-based response theory formulation that allows for the use of both time- and perturbation-dependent basis sets [Thorvaldsen, Ruud, Kristensen, Jo̸rgensen, and Coriani, J. Chem. Phys. 129, 214108 (2008)]. We present the detailed expressions for the response functions entering the Jones birefringence when London atomic orbitals are used. The implementation is tested on a set of polar and dipolar molecules at the Hartree-Fock level of theory. It is demonstrated that London orbitals lead to much improved basis-set convergence, and that the use of small, conventional basis sets may lead to the wrong sign for the calculated birefringence. For large basis sets, London orbitals and conventional basis sets converge to the same results.
我们提出了在哈特ree-fock 理论水平上琼斯双折射的第一个规范原点独立的表述。通过使用伦敦原子轨道实现了规范原点的独立性。该实现基于最近提出的基于原子轨道的响应理论表述，允许使用时间和微扰相关的基组[thorvaldsen、rud、kristensen、jørgensen 和 coriani，j.chem.phys.129,214108(2008)]。我们给出了在使用伦敦原子轨道时，进入琼斯双折射的响应函数的详细表达式。该实现是在一组极和偶极分子的哈特ree-fock 理论水平上进行测试的。结果表明，伦敦轨道导致了更好的基组收敛性，并且使用小的常规基组可能导致计算出的双折射的符号错误。对于大的基组，伦敦轨道和常规基组收敛到相同的结果。
