Journal article
U and P-4 Reaction Products: A Quantum Chemical and Matrix Isolation Spectroscopic Investigation
Inorganic chemistry, Vol.49(20), pp.9230-9235
10/18/2010
DOI: 10.1021/ic100407e
PMID: 20843087
Abstract
Reactions of laser-ablated U atoms with P-4 molecules upon codeposition in excess argon gave weak new infrared absorptions at 504, 483, and 426 cm(-1), which are best identified as binary uranium phosphide UP4 species based on extensive B3LYP, BPW91, and PBE density functional and CASSCF/CASPT2 wave function based calculations. These UP4 adducts may be considered as simple models for P4 activation products by ligand-supported transition and main group metal complexes. The sought-after PUP molecule in the (3)Phi(u) ground state probably absorbs under the intense P4 precursor band near 465 cm-1. The triplet U(IV) molecule PUP is 7 kcal/mol lower in energy than the U(VI) analog, singlet PUP. The (3)Phi(u) ground state of PUP, with 2,54 effective bond order computed by CASPT2, may be compared to the (1)Sigma(+)(g) ground state of N U N with 2.87 effective bond order, where third row elements are less effective for pi bond formation than second row elements.
Details
- Title: Subtitle
- U and P-4 Reaction Products: A Quantum Chemical and Matrix Isolation Spectroscopic Investigation
- Creators
- Bess Vlaisavljevich - University of Minnesota, DuluthLaura Gagliardi - Pittsburgh Supercomputing CenterXuefeng Wang - University of VirginiaBinyong Liang - University of VirginiaLester Andrews - University of VirginiaIvan Infante - Donostia International Physics Center
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.49(20), pp.9230-9235
- Publisher
- Amer Chemical Soc
- DOI
- 10.1021/ic100407e
- PMID
- 20843087
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Number of pages
- 6
- Grant note
- CHE07-0004N / NCSA DE-SC0001034; DE-SC002183 / DOE; United States Department of Energy (DOE) 200020-120007 / Swiss National Science Foundation; Swiss National Science Foundation (SNSF)
- Language
- English
- Date published
- 10/18/2010
- Academic Unit
- Chemistry
- Record Identifier
- 9984618637102771
Metrics
5 Record Views