Back to Search
Start Over
Quasirelativistic theory for magnetic shielding constants. II. Gauge-including atomic orbitals and applications to molecules
- Source :
- JOURNAL OF CHEMICAL PHYSICS. 118(3):1027-1035
- Publication Year :
- 2003
- Publisher :
- AMER INST PHYSICS, 2003.
-
Abstract
- Quasirelativistic theory of magnetic shielding constants based on the Douglas–Kroll–Hess transformation of the magnetic potential presented in a previous paper is extended to molecular systems that contain heavy elements. The gauge-including atomic orbital method is adapted to the quasirelativistic Hamiltonian to allow origin-independent calculations. The present theory is applied to the proton and halogen magnetic shielding constants of hydrogen halides and the 199Hg magnetic shielding constants and chemical shifts of mercury dihalides and methyl mercury halides. While the relativistic correction to the magnetic interaction term has little effect on the proton magnetic shielding constants, this correction is a dominant origin of the heavy atom shifts of the magnetic shielding constants of heavy halogens and mercury. The basis set-dependence of mercury shielding constants is quite large in the relativistic calculation; it is important to use the basis functions that are optimized by the relativistic metho...
- Subjects :
- Hydrogen
Chemistry
Chemical shift
General Physics and Astronomy
chemistry.chemical_element
symbols.namesake
Atomic orbital
Electromagnetic shielding
symbols
Shielding effect
Molecule
Physics::Atomic Physics
Magnetic potential
Physical and Theoretical Chemistry
Atomic physics
Hamiltonian (quantum mechanics)
Subjects
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 118
- Issue :
- 3
- Database :
- OpenAIRE
- Journal :
- JOURNAL OF CHEMICAL PHYSICS
- Accession number :
- edsair.doi.dedup.....80abc212e6e75e79fed904538e97d77e