Interaction of Th with H0/–/+: Combined Experimental and Theoretical Thermodynamic Properties

Vasiliu, Monica; Peterson, Kirk A.; Marshall, Mary; Zhu, Zhaoguo; Tufekci, Burak A.; Bowen, Kit H.; Dixon, David A.

doi:10.1021/acs.jpca.1c07598

Title: Interaction of Th with H^0/–/+: Combined Experimental and Theoretical Thermodynamic Properties

Journal Article · 06 January 2022 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.1c07598 · OSTI ID:1909827

Vasiliu, Monica ^[1];

^[2]; Marshall, Mary ^[3];

^[3]; Tufekci, Burak A. ^[3];

^[3];

^[4]

Univ. of Alabama, Tuscaloosa, AL (United States); The Johns Hopkins University
Washington State Univ., Pullman, WA (United States)
Johns Hopkins Univ., Baltimore, MD (United States)
Univ. of Alabama, Tuscaloosa, AL (United States)

In this work, high-level electronic structure calculations of the lowlying energy electronic states for ThH, ThH^–, and ThH⁺ are reported and compared to experimental measurements. The inclusion of spin–orbit coupling is critical to predict the ground-state ordering as inclusion of spin–orbit switches the coupled-cluster CCSD(T) ordering of the two lowest energy states for ThH and ThH⁺. At the multireference spin–orbit SO-CASPT2 level, the ground states of ThH, ThH^–, and ThH⁺ are predicted to be the ²Δ_3/2, ³Φ₂, and ³Δ₁ states, respectively. The adiabatic electron affinity is calculated to be 0.820 eV, and the vertical detachment energy is calculated to be 0.832 eV in comparison to an experimental value of 0.87 ± 0.02 eV. The observed ThH^– photoelectron spectrum has many transitions, which approximately correlate with excitations of Th⁺ and/or Th. The adiabatic ionization energy of ThH including spin–orbit corrections is calculated to be 6.181 eV. The natural bond orbital results are consistent with a significant contribution of the Th⁺H^– ionic configuration to the bonding in ThH. The bond dissociation energies for ThH, ThH^–, and ThH⁺ using the Feller–Peterson–Dixon approach were calculated to be similar for all three molecules and lie between 259 and 280 kJ/mol.

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Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

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

Grant/Contract Number:: SC0019317; SC0018921; SC0008501

OSTI ID:: 1909827

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 2 Vol. 126; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

ThH ₅ : An Actinide‐Containing Superhalogen Molecule Marshall, Mary; Zhu, Zhaoguo; Harris, Rachel ChemPhysChem, Vol. 22, Issue 1 https://doi.org/10.1002/cphc.202000918	journal	December 2020
NBO 7.0 : New vistas in localized and delocalized chemical bonding theory Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank Journal of Computational Chemistry https://doi.org/10.1002/jcc.25873	journal	June 2019
Chemical accuracy in ab initio thermochemistry and spectroscopy: current strategies and future challenges Peterson, Kirk A.; Feller, David; Dixon, David A. Theoretical Chemistry Accounts, Vol. 131, Issue 1 https://doi.org/10.1007/s00214-011-1079-5	journal	January 2012
Quantum electrodynamical corrections to the fine structure of helium Douglas, Marvin; Kroll, Norman M. Annals of Physics, Vol. 82, Issue 1 https://doi.org/10.1016/0003-4916(74)90333-9	journal	January 1974
Passing the one-billion limit in full configuration-interaction (FCI) calculations Olsen, Jeppe; Jørgensen, Poul; Simons, Jack Chemical Physics Letters, Vol. 169, Issue 6 https://doi.org/10.1016/0009-2614(90)85633-n	journal	June 1990
Perturbative corrections to account for triple excitations in closed and open shell coupled cluster theories Deegan, Miles J. O.; Knowles, Peter J. Chemical Physics Letters, Vol. 227, Issue 3 https://doi.org/10.1016/0009-2614(94)00815-9	journal	September 1994
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
Large-scale electron correlation calculations in the framework of the spin-free dirac formalism: the Au2 molecule revisited Fleig, T.; Visscher, L. Chemical Physics, Vol. 311, Issue 1-2 https://doi.org/10.1016/j.chemphys.2004.10.003	journal	April 2005
A modified definition of the zeroth-order Hamiltonian in multiconfigurational perturbation theory (CASPT2) Ghigo, Giovanni; Roos, Björn O.; Malmqvist, Per-Åke Chemical Physics Letters, Vol. 396, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.08.032	journal	September 2004
A fifth-order perturbation comparison of electron correlation theories Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A. Chemical Physics Letters, Vol. 157, Issue 6 https://doi.org/10.1016/s0009-2614(89)87395-6	journal	May 1989
Guided Ion Beam Studies of the Thorium Monocarbonyl Cation Bond Dissociation Energy and Theoretical Unveiling of Different Isomers of [Th,O,C] ⁺ and Their Rearrangement Mechanism Kafle, Arjun; Armentrout, P. B.; Battey, Samuel R. Inorganic Chemistry, Vol. 60, Issue 14 https://doi.org/10.1021/acs.inorgchem.1c01012	journal	July 2021
Activation of CH ₄ by Th ⁺ as Studied by Guided Ion Beam Mass Spectrometry and Quantum Chemistry Cox, Richard M.; Armentrout, P. B.; de Jong, Wibe A. Inorganic Chemistry, Vol. 54, Issue 7 https://doi.org/10.1021/acs.inorgchem.5b00137	journal	March 2015
Guided Ion Beam and Quantum Chemical Investigation of the Thermochemistry of Thorium Dioxide Cations: Thermodynamic Evidence for Participation of f Orbitals in Bonding Armentrout, P. B.; Peterson, Kirk A. Inorganic Chemistry, Vol. 59, Issue 5 https://doi.org/10.1021/acs.inorgchem.9b03488	journal	February 2020
Th ₂ O ^– , Th ₂ Au ^– , and Th ₂ AuO _1,2 ^– Anions: Photoelectron Spectroscopic and Computational Characterization of Energetics and Bonding Zhu, Zhaoguo; Marshall, Mary; Harris, Rachel M. The Journal of Physical Chemistry A, Vol. 125, Issue 1 https://doi.org/10.1021/acs.jpca.0c09766	journal	December 2020
Gas Phase Properties of MX ₂ and MX ₄ (X = F, Cl) for M = Group 4, Group 14, Cerium, and Thorium Thanthiriwatte, K. Sahan; Vasiliu, Monica; Battey, Samuel R. The Journal of Physical Chemistry A, Vol. 119, Issue 22 https://doi.org/10.1021/acs.jpca.5b02544	journal	May 2015
Active Thermochemical Tables: The Adiabatic Ionization Energy of Hydrogen Peroxide Changala, P. Bryan; Nguyen, T. Lam; Baraban, Joshua H. The Journal of Physical Chemistry A, Vol. 121, Issue 46 https://doi.org/10.1021/acs.jpca.7b06221	journal	September 2017
Optical Stark and Zeeman Spectroscopy of Thorium Fluoride (ThF) and Thorium Chloride (ThCl) Nguyen, Duc-Trung; Steimle, Timothy; Linton, Colan The Journal of Physical Chemistry A, Vol. 123, Issue 7 https://doi.org/10.1021/acs.jpca.8b11853	journal	November 2018
Reactions of Th ⁺ + H ₂ , D ₂ , and HD Studied by Guided Ion Beam Tandem Mass Spectrometry and Quantum Chemical Calculations Cox, Richard M.; Armentrout, P. B.; de Jong, Wibe A. The Journal of Physical Chemistry B, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcb.5b08008	journal	October 2015
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank Chemical Reviews, Vol. 88, Issue 6 https://doi.org/10.1021/cr00088a005	journal	September 1988
An open-shell spin-restricted coupled cluster method: application to ionization potentials in nitrogen Rittby, Magnus; Bartlett, Rodney J. The Journal of Physical Chemistry, Vol. 92, Issue 11 https://doi.org/10.1021/j100322a004	journal	June 1988
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
Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited ^† Ruscic, Branko; Pinzon, Reinhardt E.; Morton, Melita L. The Journal of Physical Chemistry A, Vol. 108, Issue 45 https://doi.org/10.1021/jp047912y	journal	November 2004
Relativistic Small-Core Pseudopotentials for Actinium, Thorium, and Protactinium Weigand, Anna; Cao, Xiaoyan; Hangele, Tim The Journal of Physical Chemistry A, Vol. 118, Issue 13 https://doi.org/10.1021/jp500215z	journal	March 2014
Infrared Spectra of ThH ₂ , ThH ₄ , and the Hydride Bridging ThH ₄ (H ₂ ) _x ( x = 1−4) Complexes in Solid Neon and Hydrogen Wang, Xuefeng; Andrews, Lester; Gagliardi, Laura The Journal of Physical Chemistry A, Vol. 112, Issue 8 https://doi.org/10.1021/jp710326k	journal	February 2008
Parallel Douglas–Kroll energy and gradients in NWChem: Estimating scalar relativistic effects using Douglas–Kroll contracted basis sets de Jong, W. A.; Harrison, R. J.; Dixon, D. A. The Journal of Chemical Physics, Vol. 114, Issue 1 https://doi.org/10.1063/1.1329891	journal	January 2001
The generalized active space concept for the relativistic treatment of electron correlation. I. Kramers-restricted two-component configuration interaction Fleig, Timo; Olsen, Jeppe; Marian, Christel M. The Journal of Chemical Physics, Vol. 114, Issue 11 https://doi.org/10.1063/1.1349076	journal	March 2001
Formulation and implementation of the relativistic Fock-space coupled cluster method for molecules Visscher, Lucas; Eliav, Ephraim; Kaldor, Uzi The Journal of Chemical Physics, Vol. 115, Issue 21 https://doi.org/10.1063/1.1415746	journal	December 2001
Cobalt–benzene cluster anions: Mass spectrometry and negative ion photoelectron spectroscopy Gerhards, M.; Thomas, O. C.; Nilles, J. M. The Journal of Chemical Physics, Vol. 116, Issue 23 https://doi.org/10.1063/1.1477924	journal	June 2002
The generalized Douglas–Kroll transformation Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur The Journal of Chemical Physics, Vol. 117, Issue 20 https://doi.org/10.1063/1.1515314	journal	November 2002
Spectroscopic investigations of ThF and ThF ⁺ Barker, Beau J.; Antonov, Ivan O.; Heaven, Michael C. The Journal of Chemical Physics, Vol. 136, Issue 10 https://doi.org/10.1063/1.3691301	journal	March 2012
The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule Siegbahn, Per E. M.; Almlöf, Jan; Heiberg, Anders The Journal of Chemical Physics, Vol. 74, Issue 4 https://doi.org/10.1063/1.441359	journal	February 1981
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples Purvis, George D.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 76, Issue 4 https://doi.org/10.1063/1.443164	journal	February 1982
The full CCSDT model for molecular electronic structure Noga, Jozef; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 86, Issue 12 https://doi.org/10.1063/1.452353	journal	June 1987
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
The coupled‐cluster single, double, and triple excitation model for open‐shell single reference functions Watts, John D.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 93, Issue 8 https://doi.org/10.1063/1.459002	journal	October 1990
Photoelectron spectroscopy of metal cluster anions: Cu ⁻ _n , Ag ⁻ _n , and Au ⁻ _n Ho, Joe; Ervin, Kent M.; Lineberger, W. C. The Journal of Chemical Physics, Vol. 93, Issue 10 https://doi.org/10.1063/1.459475	journal	November 1990
Second‐order perturbation theory with a complete active space self‐consistent field reference function Andersson, Kerstin; Malmqvist, Per‐Åke; Roos, Björn O. The Journal of Chemical Physics, Vol. 96, Issue 2 https://doi.org/10.1063/1.462209	journal	January 1992
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients Watts, John D.; Gauss, Jürgen; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 98, Issue 11 https://doi.org/10.1063/1.464480	journal	June 1993
Coupled cluster theory for high spin, open shell reference wave functions Knowles, Peter J.; Hampel, Claudia; Werner, Hans‐Joachim The Journal of Chemical Physics, Vol. 99, Issue 7 https://doi.org/10.1063/1.465990	journal	October 1993
An exact separation of the spin‐free and spin‐dependent terms of the Dirac–Coulomb–Breit Hamiltonian Dyall, Kenneth G. The Journal of Chemical Physics, Vol. 100, Issue 3 https://doi.org/10.1063/1.466508	journal	February 1994
Benchmark calculations with correlated molecular wave functions. IV. The classical barrier height of the H+H ₂ →H ₂ +H reaction Peterson, Kirk A.; Woon, David E.; Dunning, Thom H. The Journal of Chemical Physics, Vol. 100, Issue 10 https://doi.org/10.1063/1.466884	journal	May 1994
Formulation and implementation of a relativistic unrestricted coupled‐cluster method including noniterative connected triples Visscher, Lucas; Lee, Timothy J.; Dyall, Kenneth G. The Journal of Chemical Physics, Vol. 105, Issue 19 https://doi.org/10.1063/1.472655	journal	November 1996
Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C. The Journal of Chemical Physics, Vol. 106, Issue 3 https://doi.org/10.1063/1.473182	journal	January 1997
Noniterative energy corrections through fifth-order to the coupled cluster singles and doubles method Kucharski, Stanisław A.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 108, Issue 13 https://doi.org/10.1063/1.475961	journal	April 1998
An efficient linear-scaling CCSD(T) method based on local natural orbitals Rolik, Zoltán; Szegedy, Lóránt; Ladjánszki, István The Journal of Chemical Physics, Vol. 139, Issue 9 https://doi.org/10.1063/1.4819401	journal	September 2013
Correlation consistent basis sets for actinides. I. The Th and U atoms Peterson, Kirk A. The Journal of Chemical Physics, Vol. 142, Issue 7 https://doi.org/10.1063/1.4907596	journal	February 2015
Bond energies of ThO ⁺ and ThC ⁺ : A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O ₂ and CO Cox, Richard M.; Citir, Murat; Armentrout, P. B. The Journal of Chemical Physics, Vol. 144, Issue 18 https://doi.org/10.1063/1.4948812	journal	May 2016
Spectroscopic and theoretical studies of ThCl and ThCl ⁺ VanGundy, Robert A.; Bartlett, Joshua H.; Heaven, Michael C. The Journal of Chemical Physics, Vol. 146, Issue 5 https://doi.org/10.1063/1.4975070	journal	February 2017
Bond energy of ThN ⁺ : A guided ion beam and quantum chemical investigation of the reactions of thorium cation with N ₂ and NO Cox, Richard M.; Kafle, Arjun; Armentrout, P. B. The Journal of Chemical Physics, Vol. 151, Issue 3 https://doi.org/10.1063/1.5111534	journal	July 2019
Erratum: The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C1 and C2 organic substances in SI units [J. Phys. Chem. Ref. Data 11, Suppl. 2 (1982)] Wagman, Donald D.; Evans, William H.; Parker, Vivian B. Journal of Physical and Chemical Reference Data, Vol. 18, Issue 4 https://doi.org/10.1063/1.555845	journal	October 1989
Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update Hunter, Edward P. L.; Lias, Sharon G. Journal of Physical and Chemical Reference Data, Vol. 27, Issue 3 https://doi.org/10.1063/1.556018	journal	May 1998
The Molpro quantum chemistry package Werner, Hans-Joachim; Knowles, Peter J.; Manby, Frederick R. The Journal of Chemical Physics, Vol. 152, Issue 14 https://doi.org/10.1063/5.0005081	journal	April 2020
The electron affinity of the uranium atom Ciborowski, Sandra M.; Liu, Gaoxiang; Blankenhorn, Moritz The Journal of Chemical Physics, Vol. 154, Issue 22 https://doi.org/10.1063/5.0046315	journal	June 2021
Spin-orbit matrix elements for internally contracted multireference configuration interaction wavefunctions Berning, Andreas; Schweizer, Marcus; Werner, Hans-Joachim Molecular Physics, Vol. 98, Issue 21 https://doi.org/10.1080/00268970009483386	journal	November 2000
Further benchmarks of a composite, convergent, statistically calibrated coupled-cluster-based approach for thermochemical and spectroscopic studies Feller, David; Peterson, Kirk A.; Dixon, David A. Molecular Physics, Vol. 110, Issue 19-20 https://doi.org/10.1080/00268976.2012.684897	journal	April 2012
Search for effective local model potentials for simulation of quantum electrodynamic effects in relativistic calculations Pyykk , Pekka; Zhao, Li-Bo Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 36, Issue 8 https://doi.org/10.1088/0953-4075/36/8/302	journal	March 2003
The Wentzel-Brillouin-Kramers Method of Solving the Wave Equation Dunham, J. L. Physical Review, Vol. 41, Issue 6 https://doi.org/10.1103/physrev.41.713	journal	September 1932
The Energy Levels of a Rotating Vibrator Dunham, J. L. Physical Review, Vol. 41, Issue 6 https://doi.org/10.1103/physrev.41.721	journal	September 1932
Revision of the Douglas-Kroll transformation Jansen, Georg; Hess, Bernd A. Physical Review A, Vol. 39, Issue 11 https://doi.org/10.1103/physreva.39.6016	journal	June 1989
Candidate for Laser Cooling of a Negative Ion: High-Resolution Photoelectron Imaging of Th − Tang, Rulin; Si, Ran; Fei, Zejie Physical Review Letters, Vol. 123, Issue 20 https://doi.org/10.1103/physrevlett.123.203002	journal	November 2019
Coupled-cluster theory in quantum chemistry Bartlett, Rodney J.; Musiał, Monika Reviews of Modern Physics, Vol. 79, Issue 1 https://doi.org/10.1103/revmodphys.79.291	journal	February 2007

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