Advanced

Infrared Spectra and Quantum Chemical Calculations of the Uranium Carbide Molecules UC and CUC with Triple Bonds.

Wang, Xuefeng; Andrews, Lester; Malmqvist, Per-Åke LU ; Roos, Björn LU ; Gonçalves, António P; Pereira, Cláudia C L; Marçalo, Joaquim; Godart, Claude and Villeroy, Benjamin (2010) In Journal of the American Chemical Society 132. p.8484-8488
Abstract
Laser evaporation of carbon-rich uranium/carbon alloys followed by atom reactions in a solid argon matrix and trapping at 8 K gives weak infrared absorptions for CUO at 852 and 804 cm−1. A new band at 827 cm−1 becomes a doublet with mixed carbon 12 and 13 isotopes and exhibits the 1.0381 isotopic frequency ratio, which is appropriate for the UC diatomic molecule, and another new band at 891 cm−1 gives a three-band mixed isotopic spectrum with the 1.0366 isotopic frequency ratio, which is characteristic of the linear CUC molecule. CASPT2 calculations with dynamical correlation find the C≡U≡C ground state as linear 3Σu+ with 1.840 Å bond length and molecular orbital occupancies for an effective bond order of 2.83. Similar calculations with... (More)
Laser evaporation of carbon-rich uranium/carbon alloys followed by atom reactions in a solid argon matrix and trapping at 8 K gives weak infrared absorptions for CUO at 852 and 804 cm−1. A new band at 827 cm−1 becomes a doublet with mixed carbon 12 and 13 isotopes and exhibits the 1.0381 isotopic frequency ratio, which is appropriate for the UC diatomic molecule, and another new band at 891 cm−1 gives a three-band mixed isotopic spectrum with the 1.0366 isotopic frequency ratio, which is characteristic of the linear CUC molecule. CASPT2 calculations with dynamical correlation find the C≡U≡C ground state as linear 3Σu+ with 1.840 Å bond length and molecular orbital occupancies for an effective bond order of 2.83. Similar calculations with spin-orbit coupling show that the U≡C diatomic molecule has a quintet (Λ = 5, Ω = 3) ground state, a similar 1.855 Å bond length, and a fully developed triple bond of 2.82 effective bond order. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
132
pages
8484 - 8488
publisher
The American Chemical Society
external identifiers
  • wos:000278905700048
  • pmid:20504028
  • scopus:77953624396
ISSN
1520-5126
DOI
10.1021/ja102475t
language
English
LU publication?
yes
id
6e31a1e0-4756-4b0b-929d-fd29e51717c0 (old id 1609913)
date added to LUP
2010-06-02 12:19:10
date last changed
2018-05-29 10:30:46
@article{6e31a1e0-4756-4b0b-929d-fd29e51717c0,
  abstract     = {Laser evaporation of carbon-rich uranium/carbon alloys followed by atom reactions in a solid argon matrix and trapping at 8 K gives weak infrared absorptions for CUO at 852 and 804 cm−1. A new band at 827 cm−1 becomes a doublet with mixed carbon 12 and 13 isotopes and exhibits the 1.0381 isotopic frequency ratio, which is appropriate for the UC diatomic molecule, and another new band at 891 cm−1 gives a three-band mixed isotopic spectrum with the 1.0366 isotopic frequency ratio, which is characteristic of the linear CUC molecule. CASPT2 calculations with dynamical correlation find the C≡U≡C ground state as linear 3Σu+ with 1.840 Å bond length and molecular orbital occupancies for an effective bond order of 2.83. Similar calculations with spin-orbit coupling show that the U≡C diatomic molecule has a quintet (Λ = 5, Ω = 3) ground state, a similar 1.855 Å bond length, and a fully developed triple bond of 2.82 effective bond order.},
  author       = {Wang, Xuefeng and Andrews, Lester and Malmqvist, Per-Åke and Roos, Björn and Gonçalves, António P and Pereira, Cláudia C L and Marçalo, Joaquim and Godart, Claude and Villeroy, Benjamin},
  issn         = {1520-5126},
  language     = {eng},
  pages        = {8484--8488},
  publisher    = {The American Chemical Society},
  series       = {Journal of the American Chemical Society},
  title        = {Infrared Spectra and Quantum Chemical Calculations of the Uranium Carbide Molecules UC and CUC with Triple Bonds.},
  url          = {http://dx.doi.org/10.1021/ja102475t},
  volume       = {132},
  year         = {2010},
}