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Title: Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of ChemistryUniversity at Buffalo State University of New York Buffalo NY 14260-3000 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1582477
Grant/Contract Number:  
SC0001136
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Name: Chemistry - A European Journal; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Ganguly, Gaurab, Sergentu, Dumitru‐Claudiu, and Autschbach, Jochen. Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States. Germany: N. p., 2020. Web. doi:10.1002/chem.201904166.
Ganguly, Gaurab, Sergentu, Dumitru‐Claudiu, & Autschbach, Jochen. Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States. Germany. doi:10.1002/chem.201904166.
Ganguly, Gaurab, Sergentu, Dumitru‐Claudiu, and Autschbach, Jochen. Mon . "Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States". Germany. doi:10.1002/chem.201904166.
@article{osti_1582477,
title = {Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States},
author = {Ganguly, Gaurab and Sergentu, Dumitru‐Claudiu and Autschbach, Jochen},
abstractNote = {},
doi = {10.1002/chem.201904166},
journal = {Chemistry - A European Journal},
number = ,
volume = ,
place = {Germany},
year = {2020},
month = {1}
}

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Works referenced in this record:

The role of databases in support of computational chemistry calculations
journal, October 1996


Quantum chemical calculations show that the uranium molecule U2 has a quintuple bond
journal, February 2005


Multiplet effects in X-ray spectroscopy
journal, January 2005


Ab Initio Study of Covalency in the Ground versus Core-Excited States and X-ray Absorption Spectra of Actinide Complexes
journal, September 2018

  • Sergentu, Dumitru-Claudiu; Duignan, Thomas J.; Autschbach, Jochen
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 18
  • DOI: 10.1021/acs.jpclett.8b02412

Organo-f-element-based heterogeneous catalysts. Kinetics and mechanism of olefin hydrogenation by supported pentamethylcyclopentadienyl actinide complexes
journal, September 1990

  • Gillespie, Ralph D.; Burwell, Robert L.; Marks, Tobin J.
  • Langmuir, Vol. 6, Issue 9
  • DOI: 10.1021/la00099a007

C-H-Aktivierung mit Komplexen der f-Block-Elemente
journal, November 2014

  • Arnold, Polly L.; McMullon, Max W.; Rieb, Julia
  • Angewandte Chemie, Vol. 127, Issue 1
  • DOI: 10.1002/ange.201404613

Small-Molecule Activation Mediated by a Uranium Bipyridyl Metallocene
journal, March 2017


Di-.pi.-cyclooctatetraenethorium
journal, December 1969

  • Streitwieser, Andrew; Yoshida, Norio
  • Journal of the American Chemical Society, Vol. 91, Issue 26
  • DOI: 10.1021/ja01054a061

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

Density matrix averaged atomic natural orbital (ANO) basis sets for correlated molecular wave functions: I. First row atoms
journal, January 1990

  • Widmark, Per-Olof; Malmqvist, Per-�ke; Roos, Bj�rn O.
  • Theoretica Chimica Acta, Vol. 77, Issue 5
  • DOI: 10.1007/BF01120130

Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994

  • Küchle, W.; Dolg, M.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 100, Issue 10
  • DOI: 10.1063/1.466847

Determinant based configuration interaction algorithms for complete and restricted configuration interaction spaces
journal, August 1988

  • Olsen, Jeppe; Roos, Björn O.; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 89, Issue 4
  • DOI: 10.1063/1.455063

Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling
journal, August 2015

  • Grell, Gilbert; Bokarev, Sergey I.; Winter, Bernd
  • The Journal of Chemical Physics, Vol. 143, Issue 7
  • DOI: 10.1063/1.4928511

Quantum electrodynamical corrections to the fine structure of helium
journal, January 1974


Exploring the Actinide−Actinide Bond:  Theoretical Studies of the Chemical Bond in Ac 2 , Th 2 , Pa 2 , and U 2
journal, December 2006

  • Roos, Björn O.; Malmqvist, Per-Åke; Gagliardi, Laura
  • Journal of the American Chemical Society, Vol. 128, Issue 51
  • DOI: 10.1021/ja066615z

Quasirelativistic SCF-X.alpha. scattered-wave study of uranocene, thorocene, and cerocene
journal, November 1983

  • Roesch, Notker; Streitwieser, Andrew
  • Journal of the American Chemical Society, Vol. 105, Issue 25
  • DOI: 10.1021/ja00363a004

Covalency in f-element complexes
journal, January 2013

  • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
  • Coordination Chemistry Reviews, Vol. 257, Issue 2
  • DOI: 10.1016/j.ccr.2012.04.029

Metal and Ligand K-Edge XAS of Organotitanium Complexes:  Metal 4p and 3d Contributions to Pre-edge Intensity and Their Contributions to Bonding
journal, January 2005

  • DeBeer George, Serena; Brant, Patrick; Solomon, Edward I.
  • Journal of the American Chemical Society, Vol. 127, Issue 2
  • DOI: 10.1021/ja044827v

Ligand K-Edge X-ray Absorption Spectroscopy:  A Direct Probe of Ligand−Metal Covalency
journal, December 2000

  • Glaser, Thorsten; Hedman, Britt; Hodgson, Keith O.
  • Accounts of Chemical Research, Vol. 33, Issue 12
  • DOI: 10.1021/ar990125c

Direkte Untersuchung von Orbitalwechselwirkungen in gelösten metallorganischen Komplexen
journal, July 2013

  • Suljoti, Edlira; Garcia-Diez, Raul; Bokarev, Sergey I.
  • Angewandte Chemie, Vol. 125, Issue 37
  • DOI: 10.1002/ange.201303310

Cost and sensitivity of restricted active-space calculations of metal L-edge X-ray absorption spectra: Effects of the Active-Space Selection on the L-Edge XAS Spectra
journal, October 2015

  • Pinjari, Rahul V.; Delcey, Mickaël G.; Guo, Meiyuan
  • Journal of Computational Chemistry, Vol. 37, Issue 5
  • DOI: 10.1002/jcc.24237

Electronic structure and spectra of uranocene
journal, March 1989

  • Chang, Agnes H. H.; Pitzer, Russell M.
  • Journal of the American Chemical Society, Vol. 111, Issue 7
  • DOI: 10.1021/ja00189a022

New Basis Set Exchange: An Open, Up-to-Date Resource for the Molecular Sciences Community
journal, October 2019

  • Pritchard, Benjamin P.; Altarawy, Doaa; Didier, Brett
  • Journal of Chemical Information and Modeling, Vol. 59, Issue 11
  • DOI: 10.1021/acs.jcim.9b00725

Beyond the bond
journal, January 2011


Dissecting Local Atomic and Intermolecular Interactions of Transition-Metal Ions in Solution with Selective X-ray Spectroscopy
journal, November 2012

  • Wernet, Philippe; Kunnus, Kristjan; Schreck, Simon
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 23
  • DOI: 10.1021/jz301486u

Unraveling the Electronic Structure of Photocatalytic Manganese Complexes by L-Edge X-ray Spectroscopy
journal, August 2015

  • Bokarev, Sergey I.; Khan, Munirah; Abdel-Latif, Mahmoud K.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 33
  • DOI: 10.1021/acs.jpcc.5b05169

Low-lying electronic states of lanthanocenes and actinocenes M(C8H8)2 (M=Nd, Tb, Yb, U)
journal, September 1997

  • Liu, Wenjian; Dolg, Michael; Fulde, Peter
  • The Journal of Chemical Physics, Vol. 107, Issue 9
  • DOI: 10.1063/1.474698

Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes
journal, September 2015


Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl 6 x ( x = 3, 2)
journal, February 2015

  • Löble, Matthias W.; Keith, Jason M.; Altman, Alison B.
  • Journal of the American Chemical Society, Vol. 137, Issue 7
  • DOI: 10.1021/ja510067v

The He-I photoelectron spectra of uranocene and thorocene
journal, May 1976


New relativistic ANO basis sets for actinide atoms
journal, June 2005


Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal-Field Models
journal, May 2014

  • Gendron, Frédéric; Páez-Hernández, Dayán; Notter, François-Paul
  • Chemistry - A European Journal, Vol. 20, Issue 26
  • DOI: 10.1002/chem.201305039

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980


Direct Observation of Molecular Orbital Mixing in a Solvated Organometallic Complex
journal, July 2013

  • Suljoti, Edlira; Garcia-Diez, Raul; Bokarev, Sergey I.
  • Angewandte Chemie International Edition, Vol. 52, Issue 37
  • DOI: 10.1002/anie.201303310

Ab Initio Wave Function-Based Determination of Element Specific Shifts for the Efficient Calculation of X-ray Absorption Spectra of Main Group Elements and First Row Transition Metals
journal, May 2018

  • Chantzis, Agisilaos; Kowalska, Joanna K.; Maganas, Dimitrios
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 7
  • DOI: 10.1021/acs.jctc.8b00249

The restricted active space (RAS) state interaction approach with spin–orbit coupling
journal, May 2002


Ligand K-edge x-ray absorption spectroscopic studies: metal-ligand covalency in a series of transition metal tetrachlorides
journal, March 1995

  • Shadle, Susan E.; Hedman, Britt; Hodgson, Keith O.
  • Journal of the American Chemical Society, Vol. 117, Issue 8
  • DOI: 10.1021/ja00113a015

Natural localized molecular orbitals
journal, August 1985

  • Reed, Alan E.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 83, Issue 4
  • DOI: 10.1063/1.449360

The role of the 5f valence orbitals of early actinides in chemical bonding
journal, July 2017

  • Vitova, T.; Pidchenko, I.; Fellhauer, D.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms16053

Are the Ground States of the Later Actinocenes Multiconfigurational? All-Electron Spin−Orbit Coupled CASPT2 Calculations on An(η 8 -C 8 H 8 ) 2 (An = Th, U, Pu, Cm)
journal, July 2009

  • Kerridge, Andrew; Kaltsoyannis, Nikolas
  • The Journal of Physical Chemistry A, Vol. 113, Issue 30
  • DOI: 10.1021/jp903912q

Combined Experimental and Ab Initio Multireference Configuration Interaction Study of the Resonant Inelastic X-ray Scattering Spectrum of CO 2
journal, August 2014

  • Maganas, Dimitrios; Kristiansen, Paw; Duda, Laurent-Claudius
  • The Journal of Physical Chemistry C, Vol. 118, Issue 35
  • DOI: 10.1021/jp505628y

State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-Ray Absorption Spectroscopy and Ab Initio Calculations
journal, August 2013


Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986


Magnetic Properties and Electronic Structures of Ar 3 U IV –L Complexes with Ar = C 5 (CH 3 ) 4 H or C 5 H 5 and L = CH 3 , NO, and Cl
journal, November 2014

  • Gendron, Frédéric; Le Guennic, Boris; Autschbach, Jochen
  • Inorganic Chemistry, Vol. 53, Issue 24
  • DOI: 10.1021/ic502365h

Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency
journal, June 2014

  • Pollock, Christopher J.; Delgado-Jaime, Mario Ulises; Atanasov, Mihail
  • Journal of the American Chemical Society, Vol. 136, Issue 26
  • DOI: 10.1021/ja504182n

Nature of the Chemical Bond of Aqueous Fe 2+ Probed by Soft X-ray Spectroscopies and ab Initio Calculations
journal, October 2013

  • Atak, Kaan; Bokarev, Sergey I.; Gotz, Malte
  • The Journal of Physical Chemistry B, Vol. 117, Issue 41
  • DOI: 10.1021/jp408212u

The multi-state CASPT2 method
journal, May 1998


Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional
journal, March 1999

  • Ernzerhof, Matthias; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 110, Issue 11
  • DOI: 10.1063/1.478401

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory
journal, January 2014

  • Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
  • Chem. Sci., Vol. 5, Issue 1
  • DOI: 10.1039/C3SC52030G

SCF-Xα scattered-wave MO study of thorocene and uranocene
journal, January 1978


Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals
journal, December 1968

  • Streitwieser, Andrew.; Mueller-Westerhoff, Ulrich.
  • Journal of the American Chemical Society, Vol. 90, Issue 26
  • DOI: 10.1021/ja01028a044

Optimized Slater-type basis sets for the elements 1-118
journal, May 2003

  • Van Lenthe, E.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 24, Issue 9
  • DOI: 10.1002/jcc.10255

Ab Initio Calculations of X-ray Spectra: Atomic Multiplet and Molecular Orbital Effects in a Multiconfigurational SCF Approach to the L-Edge Spectra of Transition Metal Complexes
journal, November 2012

  • Josefsson, Ida; Kunnus, Kristjan; Schreck, Simon
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 23
  • DOI: 10.1021/jz301479j

Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides
journal, September 2013

  • Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
  • Journal of the American Chemical Society, Vol. 135, Issue 39
  • DOI: 10.1021/ja405844j

The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry
journal, July 1991

  • Pepper, Melanie.; Bursten, Bruce E.
  • Chemical Reviews, Vol. 91, Issue 5
  • DOI: 10.1021/cr00005a005

Selective Oligomerization and [2 + 2 + 2] Cycloaddition of Terminal Alkynes from Simple Actinide Precatalysts
journal, August 2015


Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds
journal, January 2005

  • Solomon, Edward I.; Hedman, Britt; Hodgson, Keith O.
  • Coordination Chemistry Reviews, Vol. 249, Issue 1-2
  • DOI: 10.1016/j.ccr.2004.03.020

Uranocene. The First Member of a New Class of Organometallic Derivatives of the f Elements
journal, July 2004


A Relativistic Study of the Electronic and Magnetic Properties of Cerocene and Thorocene and Its Anions
journal, April 2012

  • Ferraro, Franklin; Barboza, Cristina Aparecida; Arratia-Pérez, Ramiro
  • The Journal of Physical Chemistry A, Vol. 116, Issue 16
  • DOI: 10.1021/jp212130q

Relativistic quantum chemical calculations show that the uranium molecule U2 has a quadruple bond
journal, October 2018


Separation of actinides from spent nuclear fuel: A review
journal, November 2016


The generalized Douglas–Kroll transformation
journal, November 2002

  • Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur
  • The Journal of Chemical Physics, Vol. 117, Issue 20
  • DOI: 10.1063/1.1515314

CH Bond Activation by f-Block Complexes
journal, November 2014

  • Arnold, Polly L.; McMullon, Max W.; Rieb, Julia
  • Angewandte Chemie International Edition, Vol. 54, Issue 1
  • DOI: 10.1002/anie.201404613

Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study
journal, January 2014

  • Engel, Nicholas; Bokarev, Sergey I.; Suljoti, Edlira
  • The Journal of Physical Chemistry B, Vol. 118, Issue 6
  • DOI: 10.1021/jp411782y

Restricted active space calculations of L-edge X-ray absorption spectra: From molecular orbitals to multiplet states
journal, September 2014

  • Pinjari, Rahul V.; Delcey, Mickaël G.; Guo, Meiyuan
  • The Journal of Chemical Physics, Vol. 141, Issue 12
  • DOI: 10.1063/1.4896373

Towards an ab initio theory for metal L-edge soft X-ray spectroscopy of molecular aggregates
journal, August 2016

  • Preuße, Marie; Bokarev, Sergey I.; Aziz, Saadullah G.
  • Structural Dynamics, Vol. 3, Issue 6
  • DOI: 10.1063/1.4961953

Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8
journal, November 2015

  • Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K.
  • Journal of Computational Chemistry, Vol. 37, Issue 5
  • DOI: 10.1002/jcc.24221

Relativistic regular two‐component Hamiltonians
journal, September 1993

  • Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466059

Multiconfigurational Second-Order Perturbation Theory Restricted Active Space (RASPT2) Method for Electronic Excited States: A Benchmark Study
journal, December 2010

  • Sauri, Vicenta; Serrano-Andrés, Luis; Shahi, Abdul Rehaman Moughal
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 1
  • DOI: 10.1021/ct100478d

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001