Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Anion photoelectron spectroscopic and relativistic coupled-cluster studies of uranyl dichloride anion, UO2Cl2–

Journal Article · · Journal of Molecular Spectroscopy
 [1];  [2];  [2];  [2];  [2]
  1. Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins University
  2. Johns Hopkins Univ., Baltimore, MD (United States)
+ Show Author Affiliations
A joint relativistic coupled-cluster and experimental photoelectron (PE) spectroscopic study of the uranyl dichloride anion, UO2Cl2–, is reported. Sophisticated electronic-structure calculations predict the photodetachment of UO2Cl2– to involve a U 5f electron and to be followed by significant geometry relaxation. Therefore, the adiabatic electron affinity (EAa) of the uranyl dichloride neutral molecule, UO2Cl2, and the vertical detachment energy (VDE) of its anion, UO2Cl2–, provide valuable information about its uranium 5f orbital energies. The EAa value was computed to be 3.15 eV. The VDE value was calculated to be 3.55 eV by augmenting the computed EAa with a shift derived from a Franck–Condon simulation using coupled-cluster potential energy surfaces. Here, the VDE, which corresponds to the highest intensity peak in the PE spectrum, was measured to be 3.69 ± 0.20 eV, in good agreement with the computed value. The origin transition in the PE spectrum, whose electron binding energy corresponds to the EAa, was assigned to the feature at 3.2 ± 0.20 eV, consistent with the computed EAa.
Research Organization:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0019317; SC0020317
OSTI ID:
1832015
Alternate ID(s):
OSTI ID: 1818578
OSTI ID: 1909823
Journal Information:
Journal of Molecular Spectroscopy, Journal Name: Journal of Molecular Spectroscopy Vol. 379; ISSN 0022-2852
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (76)

The“Bare” Uranyl(2+) Ion, UO22+ journal May 1996
Single-Electron Uranyl Reduction by a Rare-Earth Cation journal December 2010
A Comparative Relativistic DFT and Ab Initio Study on the Structure and Thermodynamics of the Oxofluorides of Uranium(IV), (V) and (VI) journal June 2007
New Reactivity of the Uranyl(VI) Ion journal November 2012
Geometries, electronic structures, and excited states of UN2, NUO+, and UO 2 2+ : a combined CCSD(T), RAS/CASPT2 and TDDFT study journal January 2011
Non-iterative fifth-order triple and quadruple excitation energy corrections in correlated methods journal February 1990
A mean-field spin-orbit method applicable to correlated wavefunctions journal March 1996
Optical spectroscopic studies of uranyl chloride UO2Cl2 journal October 1994
A comparative theoretical study of bonding in UO2++,UO2+,UO2,UO2−, OUCO, O2U(CO)2 and UO2CO3 journal July 2002
A fifth-order perturbation comparison of electron correlation theories journal May 1989
On the bonding and the electric field gradient of the uranyl ion journal January 1998
Pentavalent uranyl complexes journal August 2009
Separation of actinides from spent nuclear fuel: A review journal November 2016
Theoretical study of UX6 and UO2X2 (X=F, Cl, Br, I) journal September 2004
Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [U VI O 2 ] 2+ journal August 2019
A Computational Assessment of Actinide Dioxide Cations AnO 2 2+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O═An═O] 2+ journal March 2020
Coupled Cluster Study of the Interactions of AnO 2 , AnO 2 + , and AnO 2 2+ (An = U, Np) with N 2 and CO journal March 2020
A Highly-Efficient Implementation of the Doktorov Recurrence Equations for Franck–Condon Calculations journal January 2016
Photodissociation and Theory to Investigate Uranium Oxide Cluster Cations journal February 2020
Probing the Electronic Structure and Chemical Bonding of Mono-Uranium Oxides with Different Oxidation States: UO x – and UO x ( x = 3–5) journal February 2016
Excitation Energies of UO 2 2+ , NUO + , and NUN Based on Equation-of-Motion Coupled-Cluster Theory with Spin–Orbit Coupling journal May 2017
The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry journal July 1991
Quantum Chemical Calculations and Experimental Investigations of Molecular Actinide Oxides journal January 2015
Theoretical Study of the Luminescent States and Electronic Spectra of UO 2 Cl 2 in an Argon Matrix journal August 2011
REX calculations. 12. Iteration parameters for the 5f-element organometallics of thorium-neptunium. Geometries of thorium dioxide and uranyl ion revisited journal May 1989
Speciation and Coordination Chemistry of Uranyl(VI)−Citrate Complexes in Aqueous Solution journal October 2003
Theoretical Investigations of Uranyl−Ligand Bonding:  Four- and Five-Coordinate Uranyl Cyanide, Isocyanide, Carbonyl, and Hydroxide Complexes journal April 2005
Systematic DFT Study of Gas Phase and Solvated Uranyl and Neptunyl Complexes [AnO 2 X 4 ] n (An = U, Np; X = F, Cl, OH, n = −2; X = H 2 O, n = +2) journal February 2006
Probing the Electronic Structure and Chemical Bonding in Tricoordinate Uranyl Complexes UO 2 X 3 – (X = F, Cl, Br, I): Competition between Coulomb Repulsion and U–X Bonding journal May 2013
Extending the Chemistry of the Uranyl Ion:  Lewis Acid Coordination to a UO Oxygen journal February 2004
The Coordination of Uranyl in Water:  A Combined Quantum Chemical and Molecular Simulation Study journal October 2005
Understanding the Structure and Formation of Uranyl Peroxide Nanoclusters by Quantum Chemical Calculations journal October 2010
Actinyl Ions in Cs 2 UO 2 Cl 4 journal December 2000
Electronic Structure and Spectra of Actinyl Ions journal April 2001
Structure and Spectra of UO 2 F 2 and Its Hydrated Species journal September 2001
Complexation of the Carbonate, Nitrate, and Acetate Anions with the Uranyl Dication:  Density Functional Studies with Relativistic Effective Core Potentials † journal December 2005
Electronic Structure and Bonding in Actinyl Ions and their Analogs journal May 2007
Formation of Bare UO 2 2+ and NUO + by Fragmentation of Gas-Phase Uranyl–Acetonitrile Complexes
  • Van Stipdonk, Michael J.; Michelini, Maria del Carmen; Plaviak, Alexandra
  • The Journal of Physical Chemistry A, Vol. 118, Issue 36 https://doi.org/10.1021/jp5066067
journal August 2014
Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O═U═O] 2+ Asymmetric Stretch journal March 2015
Benchmarking Electronic Structure Calculations on the Bare UO 2 2+ Ion: How Different are Single and Multireference Electron Correlation Methods? † journal November 2009
Electronic Spectroscopy of UO 2 Cl 2 Isolated in Solid Ar † journal November 2009
Hydration of UO 2 2+ and PuO 2 2+ journal March 1999
Application of Relativistic Quantum Chemistry to the Electronic Energy Levels of the Uranyl Ion journal August 1999
Reduction and selective oxo group silylation of the uranyl dication journal January 2008
Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation journal February 2012
Uranyl oxo activation and functionalization by metal cation coordination journal November 2010
Ultrafast Laser Filament-induced Fluorescence Spectroscopy of Uranyl Fluoride journal August 2018
Spectroscopic properties of uranyl chloride complexes in non-aqueous solvents journal January 2004
Electronic spectra of uranyl chloride complexes in acetone: a CASSCF/CASPT2 investigation journal January 2006
Giant spin–orbit effects on 1 H and 13 C NMR shifts for uranium( vi ) complexes revisited: role of the exchange–correlation response kernel, bonding analyses, and new predictions journal January 2016
Electronic spectroscopy of UO22+, NUO+ and NUN: an evaluation of time-dependent density functional theory for actinides journal January 2011
Interfacing relativistic and nonrelativistic methods. IV. One- and two-electron scalar approximations journal November 2001
Cobalt–benzene cluster anions: Mass spectrometry and negative ion photoelectron spectroscopy journal June 2002
Electronic structure and spectrum of UO22+ and UO2Cl42− journal November 2005
Quasirelativistic theory equivalent to fully relativistic theory journal December 2005
An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation journal February 2007
Electronic spectrum of UO22+ and [UO2Cl4]2− calculated with time-dependent density functional theory journal May 2007
A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species journal September 2007
Exact two-component Hamiltonians revisited journal July 2009
Analytic energy gradients for the spin-free exact two-component theory using an exact block diagonalization for the one-electron Dirac Hamiltonian journal August 2011
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Photoelectron spectroscopy of metal cluster anions: Cu − n , Ag − n , and Au − n journal November 1990
Reactions of pulsed‐laser evaporated uranium atoms with molecular oxygen: Infrared spectra of UO, UO 2 , UO 3 , UO 2 + , UO 2 2+ , and UO 3 –O 2 in solid argon journal March 1993
Equation of motion coupled cluster method for electron attachment journal March 1995
Interfacing relativistic and nonrelativistic methods. I. Normalized elimination of the small component in the modified Dirac equation journal June 1997
Basis-set convergence of correlated calculations on water journal June 1997
Photoelectron spectroscopy and the electronic structure of the uranyl tetrachloride dianion: UO 2 Cl 4 2− journal August 2012
The equilibrium structure and fundamental vibrational frequencies of dioxirane journal May 1998
Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes journal July 2014
High resolution photoelectron imaging of UO− and UO2− and the low-lying electronic states and vibrational frequencies of UO and UO2 journal December 2014
Correlation consistent basis sets for actinides. I. The Th and U atoms journal February 2015
Vibrational properties of anhydrous and partially hydrated uranyl fluoride journal January 2017
Two-component relativistic coupled-cluster methods using mean-field spin-orbit integrals journal January 2018
An atomic mean-field spin-orbit approach within exact two-component theory for a non-perturbative treatment of spin-orbit coupling journal April 2018
A study of non-iterative triples contributions in relativistic equation-of-motion coupled-cluster calculations using an exact two-component Hamiltonian with atomic mean-field spin-orbit integrals: Application to uranyl and other heavy-element compounds journal September 2019
Coupled-cluster techniques for computational chemistry: The CFOUR program package journal June 2020

Similar Records

Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC+/0/–
Journal Article · Sun Dec 11 19:00:00 EST 2022 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1909836

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY
Anion photoelectron
Coupled-cluster
Uranyl