PMID- 30668099
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20190225
LR  - 20190225
IS  - 1520-5215 (Electronic)
IS  - 1089-5639 (Linking)
VI  - 123
IP  - 7
DP  - 2019 Feb 21
TI  - Optical Stark and Zeeman Spectroscopy of Thorium Fluoride (ThF) and Thorium 
      Chloride (ThCl).
PG  - 1423-1433
LID - 10.1021/acs.jpca.8b11853 [doi]
AB  - Experimentally and theoretically determined magnetic and electric dipole moments, 
      bond distances, and vibrational spacings are used for a comparative study of the 
      bonding in ThF and ThCl. Numerous bands in the visible electronic spectra between 
      16 400 and 18 800 cm(-1) of supersonically cooled molecular beam samples have 
      been detected using medium-resolution (Deltanu  approximately  0.1 cm(-1)) 2D spectroscopy. 
      High-resolution (Deltanu < 20 MHz) field-free, Stark, and Zeeman spectroscopy of the 
      detected [18.6]Omega = 3/2 - X(2)Delta(3/2) band of ThF near 538.4 nm and the [18.2]Omega = 
      3/2 - X(2)Delta(3/2) band of ThCl near 551.0 nm have been recorded and analyzed. 
      Stark shifts and splitting were analyzed to produce | mu⃗(el)| values of 1.453(7) 
      D and 0.588(9) D for the X(2)Delta(3/2) and [18.6]Omega = 3/2 states of ThF, 
      respectively, and 2.022(35) D and 3.020(55) D for the X(2)Delta(3/2) and [18.2]Omega = 
      3/2 states of ThCl. Zeeman splittings and shifts were analyzed to produce g(e) 
      values of 1.038(4) and 1.079(4) for the X(2)Delta(3/2) and [18.6]Omega = 3/2 states of 
      ThF and 1.130(4) and 1.638(4) for the X(2)Delta(3/2)and [18.2]Omega = 3/2 states of ThCl. 
      Analysis of g(e) values demonstrates that the X(2)Delta(3/2) and [18.6]Omega = 3/2 states 
      of ThF and the X(2)Delta(3/2) state of ThCl are predominately (2)Delta(3/2) spin-orbit 
      components, whereas the [18.2]Omega = 3/2 state of ThCl is an admixture of (2)Delta(3/2) 
      and (2)Pi(3/2) spin-orbit components. A molecular orbital description of the 
      ground states is used to rationalize the observed | mu⃗(el)|values for the ThX (X 
      = F, Cl, O, and S) series and garner insight into the bonding mechanism. The 
      dipole moments in the ground state of ThF and ThCl have been calculated using 
      relativistic coupled-cluster methods. It is demonstrated that the systematic 
      inclusion of electron-correlation contributions plays an essential role in 
      obtaining accurate predictions for the dipole-moment values in ThF and ThCl.
FAU - Nguyen, Duc-Trung
AU  - Nguyen DT
AD  - School of Molecular Sciences , Arizona State University Tempe , Arizona 
      85287-1604 , United States.
FAU - Steimle, Timothy
AU  - Steimle T
AUID- ORCID: 0000-0002-5859-9461
AD  - School of Molecular Sciences , Arizona State University Tempe , Arizona 
      85287-1604 , United States.
FAU - Linton, Colan
AU  - Linton C
AD  - Physics Department , University of New Brunswick, 8 Bailey Drive , Fredericton , 
      New Brunswick E3B5A3 , Canada.
FAU - Cheng, Lan
AU  - Cheng L
AD  - Department of Chemistry , The Johns Hopkins University , Baltimore , Maryland 
      21218 , United States.
LA  - eng
PT  - Journal Article
DEP - 20190207
PL  - United States
TA  - J Phys Chem A
JT  - The journal of physical chemistry. A
JID - 9890903
EDAT- 2019/01/23 06:00
MHDA- 2019/01/23 06:01
CRDT- 2019/01/23 06:00
PHST- 2019/01/23 06:00 [pubmed]
PHST- 2019/01/23 06:01 [medline]
PHST- 2019/01/23 06:00 [entrez]
AID - 10.1021/acs.jpca.8b11853 [doi]
PST - ppublish
SO  - J Phys Chem A. 2019 Feb 21;123(7):1423-1433. doi: 10.1021/acs.jpca.8b11853. Epub 
      2019 Feb 7.