A new solution for the gauge origin problem

✍ Scribed by Andrzej J. Sadlej

• Publisher: Elsevier Science
• Year: 1975
• Tongue: English
• Weight: 480 KB
• Volume: 36
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(75)85705-8

✦ Synopsis

Ret&veil 30 Jlme 1975

A variation scheine for the detestation of the optizzd gauge origin in the finite basis set ~cu~tiofls of second-order molecular magnetic properties, is presented. The best gauge origin ir defied in terms of the smallest possibfe violation of the completeness r&lion for a pair of hermitean operators relevant for agiven %cond-Oider mqqetic property. In cantrast to same previous proposals, the present scheme ~pli~tIy rn~~~es the basis set error of the computes second-order energy and the best sauge origin may not coincide with the electronic centroid. The tatter only maximizes the diamagnetic mntribution to the magnetic susceptibility tensor. The proposed method is illustrated by the calculation of the proton and fluorine shielding constant for the HF motecule. * This tesearcb was rupporied by the Jxstitute of Low Tempsratures and Structure Research of the Potis& Aademy of Sciencx and by the institute of Xfathematics of the Polish Academy. of S&noes. ** TSze us1 of the London (gauge-invariant) orbif& [3j IP