Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 120, Issue 13, Pages 2150-2159Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.6b01507
Keywords
-
Funding
- JST, CREST
- JSPS KAKENHI Grant [25810007]
- US Department of Energy, Basic Energy Sciences, Geosciences, and Biosciences to the Ames Laboratory
- Iowa State University [DE-AC01-07CH11358]
- Grants-in-Aid for Scientific Research [25810007] Funding Source: KAKEN
Ask authors/readers for more resources
Methodologies beyond the Born-Oppenheimer (BO) approximation are nowadays important to explain high precision spectroscopic measurements. Most previous evaluations of the BO correction are, however, focused on light-element molecules and based on a nonrelativistic Hamiltonian, so no information about the BO approximation (BOA) breakdown in heavy-element molecules is available. The present work is the first to investigate the BOA breakdown for the entire periodic table, by considering scalar relativistic effects in the Diagonal BO correction (DBOC). In closed shell atoms, the relativistic E-DBOC scales as Z(1.25) and the nonrelativistic E-DBOC scales as Z(1.17), where Z is the atomic number. Hence, we found that E-DBOC becomes larger in heavy element atoms and molecules, and the relativistic E-DBOC increases faster than nonrelativistic E-DBOC. We have further investigated the DBOC effects on properties such as potential energy curves, spectroscopic parameters, and various energetic properties. The DBOC effects for these properties are mostly affected by the lightest atom in the molecule. Hence, in X-2 or XAt molecule (X = H, Li, Na, K, Rb, and Cs) the effect of DBOC systematically decreases when X becomes heavier but in HX molecules, the effect of DBOC seems relatively similar among all the molecules.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available