Theoretical Prediction and Interpretation of 237Np Mössbauer Isomer Shifts

Motta, Laura C.; Autschbach, Jochen

doi:10.1021/acs.jctc.1c00687

Theoretical Prediction and Interpretation of ²³⁷Np Mössbauer Isomer Shifts

Journal Article · Wed Sep 22 00:00:00 EDT 2021 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.1c00687· OSTI ID:2478534

^[1]; ^[1]

University at Buffalo, State University of New York, NY (United States)

Different theoretical approaches for the calculation of ²³⁷Np Mössbauer isomer shifts are investigated. The traditional contact density route is compared to a previously proposed alternative approach that uses energy derivatives with respect to the nuclear radius. Both approaches yield similar results as long as suitable basis sets augmented with large exponents and relativistic methods are used. Density functional theory (DFT) calculations do not show a strong dependency of the ²³⁷Np isomer shift on the chosen functional. Wavefunction calculations show that dynamic electron correlation can be important when covalent bonding influences the isomer shift. Effects from spin–orbit coupling are small. The isomer shifts of ionic solids and Np(III) organometallic complexes are largely governed by the oxidation state of Np. Isomer shifts of organometallic Np(IV) complexes are strongly affected by donation bonding. Furthermore, detailed analysis of the wavefunction results with different active spaces demonstrates that correlation among the outer core Np and occupied ligand frontier orbitals contributes significantly to isomer shifts of Np(IV) compounds.

View Accepted Manuscript (DOE)

Research Organization:: University at Buffalo, State University of New York, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001136

OSTI ID:: 2478534

Alternate ID(s):: OSTI ID: 1977911

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 10 Vol. 17; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (80)

Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L ₃ ‐edge Puzzle Sergentu, Dumitru‐Claudiu; Booth, Corwin H.; Autschbach, Jochen Chemistry – A European Journal, Vol. 27, Issue 25 https://doi.org/10.1002/chem.202100145	journal	March 2021
Dependence of relativistic effects on electronic configuration in the neutral atoms of d- and f-block elements Autschbach, J.; Siekierski, S.; Seth, M. Journal of Computational Chemistry, Vol. 23, Issue 8 https://doi.org/10.1002/jcc.10060	journal	April 2002
Optimized Slater-type basis sets for the elements 1-118 Van Lenthe, E.; Baerends, E. J. Journal of Computational Chemistry, Vol. 24, Issue 9 https://doi.org/10.1002/jcc.10255	journal	May 2003
Even-tempered slater-type orbitals revisited: From hydrogen to krypton Chong, Delano P.; Van Lenthe, Erik; Van Gisbergen, Stan Journal of Computational Chemistry, Vol. 25, Issue 8 https://doi.org/10.1002/jcc.20030	journal	January 2004
Dirac–Fock Atomic Electronic Structure Calculations Using Different Nuclear Charge Distributions Visscher, L.; Dyall, K. G. Atomic Data and Nuclear Data Tables, Vol. 67, Issue 2 https://doi.org/10.1006/adnd.1997.0751	journal	November 1997
Methodology of the Np237 Mössbauer Effect Pillinger, W. L.; Stone, J. A. Mössbauer Effect Methodology https://doi.org/10.1007/978-1-4757-1550-7_13	book	January 1968
Density matrix averaged atomic natural orbital (ANO) basis sets for correlated molecular wave functions: I. First row atoms Widmark, Per-Olof; Malmqvist, Per-�ke; Roos, Bj�rn O. Theoretica Chimica Acta, Vol. 77, Issue 5 https://doi.org/10.1007/BF01120130	journal	January 1990
Systematic trends in the237neptunium Mössbauer isomer shift: Overlap of IV, V and VI neptunium oxidation states and correlation between isomer shift and crystal structure Jové, J.; Cousson, A.; Abazli, H. Hyperfine Interactions, Vol. 39, Issue 1 https://doi.org/10.1007/BF02394642	journal	January 1988
Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the actinides Ac–Lr Dyall, Kenneth G. Theoretical Chemistry Accounts, Vol. 117, Issue 4 https://doi.org/10.1007/s00214-006-0175-4	journal	October 2006
Mössbauer spectroscopy for heavy elements: a relativistic benchmark study of mercury Knecht, Stefan; Fux, Samuel; van Meer, Robert Theoretical Chemistry Accounts, Vol. 129, Issue 3-5 https://doi.org/10.1007/s00214-011-0911-2	journal	March 2011
Chemical Information revealed by Mössbauer spectroscopy and DFT calculations Nakashima, Satoru Hyperfine Interactions, Vol. 238, Issue 1 https://doi.org/10.1007/s10751-017-1415-9	journal	February 2017
Benchmark study of DFT with Eu and Np Mössbauer isomer shifts using second-order Douglas-Kroll-Hess Hamiltonian Kaneko, Masashi; Watanabe, Masayuki; Miyashita, Sunao Hyperfine Interactions, Vol. 239, Issue 1 https://doi.org/10.1007/s10751-018-1495-1	journal	February 2018
A mean-field spin-orbit method applicable to correlated wavefunctions Heß, Bernd A.; Marian, Christel M.; Wahlgren, Ulf Chemical Physics Letters, Vol. 251, Issue 5-6 https://doi.org/10.1016/0009-2614(96)00119-4	journal	March 1996
Crystal chemistry and 237Np mössbauer investigations of neptunyl(vi) carbonate NpO2CO3 Thevenin, T.; Jove, J.; Madic, C. Journal of the Less Common Metals, Vol. 121 https://doi.org/10.1016/0022-5088(86)90565-5	journal	July 1986
The lamb shift in hydrogen-like atoms, 1 ⩽ Z ⩽ 110 Johnson, W. R.; Soff, Gerhard Atomic Data and Nuclear Data Tables, Vol. 33, Issue 3 https://doi.org/10.1016/0092-640X(85)90010-5	journal	November 1985
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M. Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1016/0301-0104(80)80045-0	journal	May 1980
Preparation, chemical reactions, and some physical properties of neptunium pentafluoride Malm, J. G.; Williams, C. W.; Soderholm, L. Journal of Alloys and Compounds, Vol. 194, Issue 1 https://doi.org/10.1016/0925-8388(93)90658-A	journal	April 1993
The restricted active space (RAS) state interaction approach with spin–orbit coupling Malmqvist, Per Åke; Roos, Björn O.; Schimmelpfennig, Bernd Chemical Physics Letters, Vol. 357, Issue 3-4 https://doi.org/10.1016/S0009-2614(02)00498-0	journal	May 2002
A model for describing paramagnetic Mössbauer relaxation spectra of organometallic 237Np compounds Adrian, G. Inorganica Chimica Acta, Vol. 139, Issue 1-2 https://doi.org/10.1016/S0020-1693(00)84109-2	journal	December 1987
Prediction and interpretation of the 57Fe isomer shift in Mössbauer spectra by density functional theory Neese, Frank Inorganica Chimica Acta, Vol. 337 https://doi.org/10.1016/S0020-1693(02)01031-9	journal	September 2002
The density-matrix renormalization group in the age of matrix product states Schollwöck, Ulrich Annals of Physics, Vol. 326, Issue 1 https://doi.org/10.1016/j.aop.2010.09.012	journal	January 2011
First principles calculation of Mössbauer isomer shift Filatov, Michael Coordination Chemistry Reviews, Vol. 253, Issue 5-6 https://doi.org/10.1016/j.ccr.2008.05.002	journal	March 2009
The Douglas–Kroll–Hess electron density at an atomic nucleus Mastalerz, Remigius; Lindh, Roland; Reiher, Markus Chemical Physics Letters, Vol. 465, Issue 1-3 https://doi.org/10.1016/j.cplett.2008.09.068	journal	November 2008
Multiconfiguration Pair-Density Functional Theory: A New Way To Treat Strongly Correlated Systems Gagliardi, Laura; Truhlar, Donald G.; Li Manni, Giovanni Accounts of Chemical Research, Vol. 50, Issue 1 https://doi.org/10.1021/acs.accounts.6b00471	journal	December 2016
Organometallic Neptunium Chemistry Arnold, Polly L.; Dutkiewicz, Michał S.; Walter, Olaf Chemical Reviews, Vol. 117, Issue 17 https://doi.org/10.1021/acs.chemrev.7b00192	journal	August 2017
A Nonorthogonal State-Interaction Approach for Matrix Product State Wave Functions Knecht, Stefan; Keller, Sebastian; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 12, Issue 12 https://doi.org/10.1021/acs.jctc.6b00889	journal	November 2016
OpenMolcas: From Source Code to Insight Fdez. Galván, Ignacio; Vacher, Morgane; Alavi, Ali Journal of Chemical Theory and Computation, Vol. 15, Issue 11 https://doi.org/10.1021/acs.jctc.9b00532	journal	September 2019
Puzzling Lack of Temperature Dependence of the PuO ₂ Magnetic Susceptibility Explained According to Ab Initio Wave Function Calculations Gendron, Frédéric; Autschbach, Jochen The Journal of Physical Chemistry Letters, Vol. 8, Issue 3 https://doi.org/10.1021/acs.jpclett.6b02968	journal	January 2017
Covalency of Neptunium(IV) Organometallics from Neptunium-237 Mössbauer Spectra Karraker, D. G. Advances in Chemistry https://doi.org/10.1021/ba-1981-0194.ch015	book	July 1981
Relativistic effects in structural chemistry Pyykko, Pekka Chemical Reviews, Vol. 88, Issue 3 https://doi.org/10.1021/cr00085a006	journal	May 1988
Electric Field Gradients Calculated from Two-Component Hybrid Density Functional Theory Including Spin−Orbit Coupling Aquino, Fredy; Govind, Niranjan; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 6, Issue 9 https://doi.org/10.1021/ct1002847	journal	August 2010
Theoretical ⁵⁷ Fe Mössbauer Spectroscopy for Structure Elucidation of [Fe] Hydrogenase Active Site Intermediates Gubler, Joël; Finkelmann, Arndt R.; Reiher, Markus Inorganic Chemistry, Vol. 52, Issue 24 https://doi.org/10.1021/ic4021349	journal	November 2013
Moessbauer and magnetic susceptibility studies of uranium(III), uranium(IV), neptunium(IV) compounds with the cyclopentadiene ion Karraker, D. G.; Stone, J. A. Inorganic Chemistry, Vol. 11, Issue 8 https://doi.org/10.1021/ic50114a004	journal	August 1972
Covalency of neptunium(IV) tris(cyclopentadienyl) compounds from Moessbauer spectra Karraker, D. G.; Stone, J. A. Inorganic Chemistry, Vol. 18, Issue 8 https://doi.org/10.1021/ic50198a031	journal	August 1979
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
Second-order perturbation theory with a CASSCF reference function Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O. The Journal of Physical Chemistry, Vol. 94, Issue 14 https://doi.org/10.1021/j100377a012	journal	July 1990
Bis(cyclooctatetraenyl)neptunium(III) and -plutonium(III) compounds Karraker, D. G.; Stone, J. A. Journal of the American Chemical Society, Vol. 96, Issue 22 https://doi.org/10.1021/ja00829a012	journal	October 1974
Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke https://doi.org/10.1021/jp031064+		December 2003
New Relativistic ANO Basis Sets for Transition Metal Atoms Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke The Journal of Physical Chemistry A, Vol. 109, Issue 29 https://doi.org/10.1021/jp0581126	journal	July 2005
Theoretical ⁵⁷ Fe Mössbauer spectroscopy: isomer shifts of [Fe]-hydrogenase intermediates Hedegård, Erik Donovan; Knecht, Stefan; Ryde, Ulf Phys. Chem. Chem. Phys., Vol. 16, Issue 10 https://doi.org/10.1039/C3CP54393E	journal	January 2014
f-Orbital covalency in the actinocenes (An = Th–Cm): multiconfigurational studies and topological analysis Kerridge, Andrew RSC Adv., Vol. 4, Issue 24 https://doi.org/10.1039/C3RA47088A	journal	January 2014
Benchmark study of the Mössbauer isomer shifts of Eu and Np complexes by relativistic DFT calculations for understanding the bonding nature of f-block compounds Kaneko, Masashi; Miyashita, Sunao; Nakashima, Satoru Dalton Transactions, Vol. 44, Issue 17 https://doi.org/10.1039/C4DT03064H	journal	January 2015
Nuclear size effects in vibrational spectra Almoukhalalati, Adel; Shee, Avijit; Saue, Trond Physical Chemistry Chemical Physics, Vol. 18, Issue 22 https://doi.org/10.1039/C6CP01913G	journal	January 2016
Mössbauer isomer shifts and effective contact densities obtained by the exact two-component (X2C) relativistic method and its local variants Zhu, Hong; Gao, Chun; Filatov, Michael Physical Chemistry Chemical Physics, Vol. 22, Issue 46 https://doi.org/10.1039/D0CP04549G	journal	January 2020
New electron correlation theories for transition metal chemistry Marti, Konrad H.; Reiher, Markus Physical Chemistry Chemical Physics, Vol. 13, Issue 15 https://doi.org/10.1039/c0cp01883j	journal	January 2011
Structural parameters and unit cell dimensions for the tetragonal actinide tetrachlorides(Th, Pa, U, and Np) and tetrabromides (Th and Pa) Brown, David; Hall, Thomas L.; Moseley, Patrick T. Journal of the Chemical Society, Dalton Transactions, Issue 6 https://doi.org/10.1039/dt9730000686	journal	January 1973
Isomer shifts in neptunium compounds Stone, J. A.; Pillinger, W. L. Symposia of the Faraday Society, Vol. 1 https://doi.org/10.1039/sf9670100077	journal	January 1967
Introduction of n -electron valence states for multireference perturbation theory Angeli, C.; Cimiraglia, R.; Evangelisti, S. The Journal of Chemical Physics, Vol. 114, Issue 23 https://doi.org/10.1063/1.1361246	journal	June 2001
Density functional investigations of the properties and thermochemistry of UF[sub n] and UCl[sub n] (n=1,…,6) Batista, Enrique R.; Martin, Richard L.; Hay, P. Jeffrey The Journal of Chemical Physics, Vol. 121, Issue 22 https://doi.org/10.1063/1.1811607	journal	January 2004
Quasirelativistic theory equivalent to fully relativistic theory Kutzelnigg, Werner; Liu, Wenjian The Journal of Chemical Physics, Vol. 123, Issue 24 https://doi.org/10.1063/1.2137315	journal	December 2005
An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation Iliaš, Miroslav; Saue, Trond The Journal of Chemical Physics, Vol. 126, Issue 6 https://doi.org/10.1063/1.2436882	journal	February 2007
On the calculation of Mössbauer isomer shift Filatov, Michael The Journal of Chemical Physics, Vol. 127, Issue 8 https://doi.org/10.1063/1.2761879	journal	August 2007
Optical and magnetic properties of the 5f[sup 1]AnX[sub 6][sup q−] series: A theoretical study Notter, François-Paul; Bolvin, Hélène The Journal of Chemical Physics, Vol. 130, Issue 18 https://doi.org/10.1063/1.3124193	journal	January 2009
Exact two-component Hamiltonians revisited Liu, Wenjian; Peng, Daoling The Journal of Chemical Physics, Vol. 131, Issue 3 https://doi.org/10.1063/1.3159445	journal	July 2009
Basis set representation of the electron density at an atomic nucleus Mastalerz, Remigius; Widmark, Per-Olof; Roos, Björn Olof The Journal of Chemical Physics, Vol. 133, Issue 14 https://doi.org/10.1063/1.3491239	journal	October 2010
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon Woon, David E.; Dunning, Thom H. The Journal of Chemical Physics, Vol. 98, Issue 2 https://doi.org/10.1063/1.464303	journal	January 1993
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Relativistic regular two‐component Hamiltonians Lenthe, E. van; Baerends, E. J.; Snijders, J. G. The Journal of Chemical Physics, Vol. 99, Issue 6 https://doi.org/10.1063/1.466059	journal	September 1993
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
Interfacing relativistic and nonrelativistic methods. I. Normalized elimination of the small component in the modified Dirac equation Dyall, Kenneth G. The Journal of Chemical Physics, Vol. 106, Issue 23 https://doi.org/10.1063/1.473860	journal	June 1997
Ab initio model potential embedded-cluster study of the ground and lowest excited states of Cr3+ defects in the elpasolites Cs2NaYCl6 and Cs2NaYBr6 Al-Abdalla, Abdalla; Barandiarán, Zoila; Seijo, Luis The Journal of Chemical Physics, Vol. 108, Issue 5 https://doi.org/10.1063/1.475610	journal	February 1998
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
Gaussian basis sets for use in correlated molecular calculations. IX. The atoms gallium through krypton Wilson, Angela K.; Woon, David E.; Peterson, Kirk A. The Journal of Chemical Physics, Vol. 110, Issue 16 https://doi.org/10.1063/1.478678	journal	April 1999
Geometry optimizations in the zero order regular approximation for relativistic effects van Lenthe, Erik; Ehlers, Andreas; Baerends, Evert-Jan The Journal of Chemical Physics, Vol. 110, Issue 18 https://doi.org/10.1063/1.478813	journal	May 1999
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Modern quantum chemistry with [Open]Molcas Aquilante, Francesco; Autschbach, Jochen; Baiardi, Alberto The Journal of Chemical Physics, Vol. 152, Issue 21 https://doi.org/10.1063/5.0004835	journal	June 2020
The DIRAC code for relativistic molecular calculations Saue, Trond; Bast, Radovan; Gomes, André Severo Pereira The Journal of Chemical Physics, Vol. 152, Issue 20 https://doi.org/10.1063/5.0004844	journal	May 2020
Relativistic atomic orbital contractions and expansions: magnitudes and explanations Baerends, E. J.; Schwarz, W. H. E.; Schwerdtfeger, P. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 23, Issue 19 https://doi.org/10.1088/0953-4075/23/19/010	journal	October 1990
Isomer Shift and Hyperfine Splittings of the 59.6-keV Mössbauer Resonance in Np 237 Dunlap, B. D.; Kalvius, G. M.; Ruby, S. L. Physical Review, Vol. 171, Issue 2 https://doi.org/10.1103/PhysRev.171.316	journal	July 1968
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Calculation of Isomer Shift in Mössbauer Spectroscopy Fricke, B.; Waber, J. T. Physical Review B, Vol. 5, Issue 9 https://doi.org/10.1103/PhysRevB.5.3445	journal	May 1972
Density matrix formulation for quantum renormalization groups White, Steven R. Physical Review Letters, Vol. 69, Issue 19 https://doi.org/10.1103/PhysRevLett.69.2863	journal	November 1992
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Crystal chemical studies of the 5f-series of elements. XII. New compounds representing known structure types Zachariasen, W. H. Acta Crystallographica, Vol. 2, Issue 6 https://doi.org/10.1107/S0365110X49001016	journal	December 1949
Effective ionic radii in oxides and fluorides Shannon, R. D.; Prewitt, C. T. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 25, Issue 5 https://doi.org/10.1107/S0567740869003220	journal	May 1969
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
A theoretical study of the structures and chemical bonds of neptunium (III) molecules by a density functional method Yin, Yao-Peng; Dong, Chen-Zhong; Du, Lei-Qiang The European Physical Journal D, Vol. 68, Issue 10 https://doi.org/10.1140/epjd/e2014-50296-x	journal	October 2014
The density matrix renormalization group for ab initio quantum chemistry Wouters, Sebastian; Van Neck, Dimitri The European Physical Journal D, Vol. 68, Issue 9 https://doi.org/10.1140/epjd/e2014-50500-1	journal	September 2014
The Density Matrix Renormalization Group in Quantum Chemistry Chan, Garnet Kin-Lic; Sharma, Sandeep Annual Review of Physical Chemistry, Vol. 62, Issue 1 https://doi.org/10.1146/annurev-physchem-032210-103338	journal	May 2011

Similar Records

²³⁷Np Mössbauer Isomer Shifts: A Lesson About the Balance of Static and Dynamic Electron Correlation in Heavy Element Complexes

Journal Article · Thu May 19 20:00:00 EDT 2022 · Journal of Chemical Theory and Computation · OSTI ID:2478533

Theoretical Evaluation of Metal–Ligand Bonding in Neptunium Compounds in Relation to ²³⁷Np Mössbauer Spectroscopy

Journal Article · Thu Aug 11 20:00:00 EDT 2022 · Inorganic Chemistry · OSTI ID:2478536

Covalency of Neptunium(IV) organometallics from /sup 237/Np Moessbauer spectra

Conference · Mon Dec 31 23:00:00 EST 1979 · OSTI ID:5541584

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Basis sets
Chemical calculations
Cluster chemistry
Electron density
Molecular structure

Theoretical Prediction and Interpretation of 237Np Mössbauer Isomer Shifts

Citation Formats

References (80)

Similar Records

Related Subjects

Theoretical Prediction and Interpretation of ²³⁷Np Mössbauer Isomer Shifts