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Title: Ab initio coupled-cluster and multi-reference configuration interaction studies of the low-lying electronic states of 1,2,3,4-cyclobutanetetraone

Journal Article · · Molecular Physics
 [1];  [1];  [1];  [2];  [3]
  1. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry
  2. Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry. Center for Advanced Scientific Computing and Modeling
  3. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry. Dept. of Physics and Astronomy
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In this paper, the four, closely spaced, lowest energy electronic states of the challenging, D4h-symmetric, 1,2,3,4-cyclobutanetetraone (C4O4) molecule have been investigated using high-level ab initio methods. The calculated states include the closed-shell singlet 8π(1A1g) state, the singlet 10π(1A1g) state, in which the π-type lowest unoccupied molecular orbital (LUMO) of the 8π(1A1g) reference is doubly occupied and the σ-type highest occupied molecular orbital (HOMO) is empty, and the open-shell singlet and triplet states, designated as 9π(1B2u) and 9π(3B2u), respectively, originating from single occupancy of the HOMO and LUMO. Our focus is on single-reference coupled-cluster (CC) approaches capable of handling electronic near-degeneracies in diradicals, especially the completely renormalised CR-CC(2,3) and active-space CCSDt methods, along with their CCSD and EOMCCSD counterparts. The internally contracted multi-reference configuration interaction calculations with a quasi-degenerate Davidson correction are performed as well. Our computations demonstrate that the state ordering is 9π(3B2u) < 8π(1A1g) < 9π(1B2u) < 10π(1A1g) and that the 8π(1A1g) - 9π(3B2u) gap is in the 7–11 kJ/mol range, in reasonable agreement with the negative ion photoelectron spectroscopy measurements, which give 6.27 ± 0.5 kJ/mol. Finally, in addition to the theory level used, geometry relaxation and basis set play a significant role in determining the state ordering and energy spacings. In particular, it is unsafe to use lower level, non-CC geometries and smaller basis sets.

Research Organization:
Michigan State Univ., East Lansing, MI (United States); Univ. of North Texas, Denton, TX (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Robert A. Welch Foundation (United States)
Grant/Contract Number:
FG02-01ER15228; CHE-0910527; B0027
OSTI ID:
1287703
Journal Information:
Molecular Physics, Vol. 114, Issue 5; ISSN 0026-8976
Publisher:
Taylor & FrancisCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

References (116)

On the Stability of the Tetramers of Carbon Monoxide, Hydrogen Isocyanide, and Vinylidene. A Molecular Orbital Theoretical Rationalization journal September 1995
Stability of Tetraoxocyclobutane Revised:  Perturbation Theory and Density Functional Scheme journal May 2001
Reinvestigation of the ordering of the low-lying electronic states of cyclobutanetetraone with CASPT2, CCSD(T), G3B3, ccCA, and CBS-QB3 calculations journal April 2009
Calculations of the Relative Energies of the 2B1g and 2A2u States of Cyclobutanetetraone Radical Cation and Radical Anion Provide Further Evidence of a 3B2u Ground State for the Neutral Molecule: A Proposed Experimental Test of the Prediction of a Triplet Ground State for (CO)4 journal August 2009
Probing the Low-Lying Electronic States of Cyclobutanetetraone (C 4 O 4 ) and Its Radical Anion: A Low-Temperature Anion Photoelectron Spectroscopic Approach journal January 2012
Negative Ion Photoelectron Spectroscopy Confirms the Prediction that (CO) 5 and (CO) 6 Each Has a Singlet Ground State journal March 2013
Singlet–triplet separations of di-radicals treated by the DEA/DIP-EOM-CCSD methods journal June 2014
Electronic structure of methylene journal February 1969
New theoretical evidence for the nonlinearity of the triplet ground state of methylene journal August 1970
Doubly electron-attached and doubly ionized equation-of-motion coupled-cluster methods with 4-particle–2-hole and 4-hole–2-particle excitations and their active-space extensions journal May 2013
Doubly electron-attached and doubly ionised equation-of-motion coupled-cluster methods with full and active-space treatments of 4-particle–2-hole and 4-hole–2-particle excitations: the role of orbital choices journal February 2014
Singlet-triplet energy gap in methylene using many-body methods journal January 1985
On the 1 A 1 – 3 B 1 separation in CH 2 and SiH 2 journal July 1987
Electron correlation, basis sets, and the methylene singlet–triplet gap journal January 1987
An ab initio calculation of ν1 and ν3 for triplet methylene (X̃ 3B1 CH2) and the determination of the vibrationless singlet–triplet splitting Te(ã 1A1) journal August 1987
Anabinitiodetermination of the potential‐energy surfaces and rotation–vibration energy levels of methylene in the lowest triplet and singlet states and the singlet–triplet splitting journal June 1989
Comparison of perturbatively corrected energy results from multiple reference double‐excitation configuration‐interaction method calculations with exact full configuration‐interaction benchmark values journal January 1990
Second-order perturbation theory with a CASSCF reference function journal July 1990
The coupled‐cluster single, double, and triple excitation model for open‐shell single reference functions journal October 1990
A state-selective quasidegenerate perturbation theory for the electronic structure of molecules journal July 1992
Second‐order perturbation theory with a complete active space self‐consistent field reference function journal January 1992
Coupled cluster theory for high spin, open shell reference wave functions journal October 1993
Full configuration interaction benchmarks for the states of methylene journal July 1997
Structures and vibrational frequencies in the full configuration interaction limit: Predictions for four electronic states of methylene using a triple-zeta plus double polarization (TZ2P) basis journal January 1998
Singlet-Triplet Splitting in Methylene: An Accurate Description of Dynamic and Nondynamic Correlation by Reduced Multireference Coupled Cluster Method journal January 1998
Electronic structure of organic diradicals: Evaluation of the performance of coupled-cluster methods journal November 2008
Third-order generalized Van Vleck perturbation theory variant of multireference perturbation theory for electron correlation journal January 2009
Excited states of methylene from quantum Monte Carlo journal September 2009
Comparison of the completely renormalized equation-of-motion coupled-cluster and Quantum Monte Carlo results for the low-lying electronic states of methylene journal October 2010
An ab initio determination of 1A1-3B1 energy gap in CH2 using orthogonally spin-adapted state-universal and state-specific coupled-cluster methods journal December 1994
Methylene: A Paradigm for Computational Quantum Chemistry journal March 1986
Methylene: A Personal Perspective book January 2009
Very-Low-Lying Electronic States Result from n → π Excitations in Open-Shell Annulenes, Annelated with α-Dicarbonyl Groups journal February 2008
Molecular Orbitals of the Oxocarbons (CO)n, n = 2–6. Why Does (CO)4 Have a Triplet Ground State? journal June 2012
Inhomogeneous Electron Gas journal November 1964
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Are atoms intrinsic to molecular electronic wavefunctions? I. The FORS model journal September 1982
The Complete Active Space Self-Consistent Field Method and its Applications in Electronic Structure Calculations book January 1987
Bound states of a many-particle system journal June 1958
Short-range correlations in nuclear wave functions journal June 1960
On the Correlation Problem in Atomic and Molecular Systems. Calculation of Wavefunction Components in Ursell‐Type Expansion Using Quantum‐Field Theoretical Methods journal December 1966
On the Use of the Cluster Expansion and the Technique of Diagrams in Calculations of Correlation Effects in Atoms and Molecules book January 2007
Correlation problems in atomic and molecular systems III. Rederivation of the coupled-pair many-electron theory using the traditional quantum chemical methodst journal July 1971
A new method for excited states: Similarity transformed equation-of-motion coupled-cluster theory journal April 1997
State Selective Equation of Motion Coupled Cluster Theory: Some Preliminary Results journal June 2002
Multireference coupled-cluster theory: The easy way journal March 2011
Multireference Double Electron Attached Coupled Cluster Method with Full Inclusion of the Connected Triple Excitations: MR-DA-CCSDT journal August 2011
Using the charge-stabilization technique in the double ionization potential equation-of-motion calculations with dianion references journal August 2011
De-perturbative corrections for charge-stabilized double ionization potential equation-of-motion coupled-cluster method journal June 2012
The equation-of-motion coupled-cluster method: Excitation energies of Be and CO journal December 1989
The equation of motion coupled‐cluster method. A systematic biorthogonal approach to molecular excitation energies, transition probabilities, and excited state properties journal May 1993
In Search of the Relationship between Multiple Solutions Characterizing Coupled-Cluster Theories book October 2000
The method of moments of coupled-cluster equations and the renormalized CCSD[T], CCSD(T), CCSD(TQ), and CCSDT(Q) approaches journal July 2000
Renormalized CCSD(T) and CCSD(TQ) approaches: Dissociation of the N2 triple bond journal October 2000
New coupled-cluster methods with singles, doubles, and noniterative triples for high accuracy calculations of excited electronic states journal January 2004
Extension of renormalized coupled-cluster methods including triple excitations to excited electronic states of open-shell molecules journal June 2005
Renormalized coupled-cluster methods exploiting left eigenstates of the similarity-transformed Hamiltonian journal December 2005
Single-reference, size-extensive, non-iterative coupled-cluster approaches to bond breaking and biradicals journal February 2006
Two new classes of non-iterative coupled-cluster methods derived from the method of moments of coupled-cluster equations journal July 2006
Extension of the Renormalized Coupled-Cluster Methods Exploiting Left Eigenstates of the Similarity-Transformed Hamiltonian to Open-Shell Systems:  A Benchmark Study † journal November 2007
Left-eigenstate completely renormalized equation-of-motion coupled-cluster methods: Review of key concepts, extension to excited states of open-shell systems, and comparison with electron-attached and ionized approaches journal November 2009
Recent advances in electronic structure theory: Method of moments of coupled-cluster equations and renormalized coupled-cluster approaches journal October 2002
Method of moments of coupled-cluster equations: a new formalism for designing accurate electronic structure methods for ground and excited states journal July 2004
Noniterative Coupled-Cluster Methods for Excited Electronic States book January 2006
Biorthogonal moment expansions in coupled-cluster theory: Review of key concepts and merging the renormalized and active-space coupled-cluster methods journal June 2012
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples journal February 1982
The linked singles and doubles model: An approximate theory of electron correlation based on the coupled‐cluster ansatz journal October 1982
Orthogonally spin-adapted coupled-cluster equations involving singly and doubly excited clusters. Comparison of different procedures for spin-adaptation journal October 1989
The closed‐shell coupled cluster single and double excitation (CCSD) model for the description of electron correlation. A comparison with configuration interaction (CISD) results journal March 1987
Combined coupled-cluster and many-body perturbation theories journal January 2004
Why CCSD(T) works: a different perspective journal December 1997
Noniterative energy corrections through fifth-order to the coupled cluster singles and doubles method journal April 1998
Perturbative corrections to coupled-cluster and equation-of-motion coupled-cluster energies: A determinantal analysis journal March 2001
Improving upon CCSD(T): ΛCCSD(T). I. Potential energy surfaces journal January 2008
Improving upon CCSD(T): ΛCCSD(T). II. Stationary formulation and derivatives journal January 2008
An efficient internally contracted multiconfiguration–reference configuration interaction method journal November 1988
An efficient method for the evaluation of coupling coefficients in configuration interaction calculations journal April 1988
The implementation of the multireference coupled‐cluster method based on the single‐reference formalism journal March 1992
A state‐selective multireference coupled‐cluster theory employing the single‐reference formalism journal August 1993
State‐selective multireference coupled‐cluster theory employing the single‐reference formalism: Implementation and application to the H 8 model system journal April 1994
State-selective multi-reference coupled-cluster theory using multi-configuration self-consistent-field orbitals. A model study on H8 journal April 1994
Breaking bonds with the state‐selective multireference coupled‐cluster method employing the single‐reference formalism journal January 1995
Improved computational strategy for the state‐selective coupled‐cluster theory with semi‐internal triexcited clusters: Potential energy surface of the HF molecule journal December 1995
Use of recursively generated intermediates in state selective multireference coupled‐cluster method: A numerical example journal December 1995
The state-selective coupled cluster method for quasi-degenerate electronic states journal May 1998
Coupled-cluster methods with internal and semi-internal triply and quadruply excited clusters: CCSDt and CCSDtq approaches journal April 1999
Coupled-cluster methods with internal and semi-internal triply excited clusters: Vibrational spectrum of the HF molecule journal October 1999
The full CCSDT model for molecular electronic structure journal June 1987
A new implementation of the full CCSDT model for molecular electronic structure journal November 1988
Multireference coupled‐cluster method using a single‐reference formalism journal January 1991
The active-space equation-of-motion coupled-cluster methods for excited electronic states: The EOMCCSDt approach journal November 2000
The active-space equation-of-motion coupled-cluster methods for excited electronic states: Full EOMCCSDt journal July 2001
Active-space coupled-cluster methods journal November 2010
Active-space equation-of-motion coupled-cluster methods for excited states of radicals and other open-shell systems: EA-EOMCCSDt and IP-EOMCCSDt journal October 2005
Extension of the active-space equation-of-motion coupled-cluster methods to radical systems: The EA-EOMCCSDt and IP-EOMCCSDt approaches journal January 2006
Efficient formulation and computer implementation of the active-space electron-attached and ionized equation-of-motion coupled-cluster methods journal December 2006
Embedding vs Supermolecular Strategies in Evaluating the Hydrogen-Bonding-Induced Shifts of Excitation Energies journal May 2011
Shifts in Excitation Energies Induced by Hydrogen Bonding: A Comparison of the Embedding and Supermolecular Time-Dependent Density Functional Theory Calculations with the Equation-of-Motion Coupled-Cluster Results book September 2011
Iterative and non-iterative triple excitation corrections in coupled-cluster methods for excited electronic states: the EOM-CCSDT-3 and EOM-CCSD(T̃) methods journal August 1996
Second- and third-order triples and quadruples corrections to coupled-cluster singles and doubles in the ground and excited states journal June 2007
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules journal March 1972
The influence of polarization functions on molecular orbital hydrogenation energies journal January 1973
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Conical intersections and double excitations in time-dependent density functional theory journal March 2006
Optimizing Conical Intersections without Derivative Coupling Vectors:  Application to Multistate Multireference Second-Order Perturbation Theory (MS-CASPT2) † journal January 2008
Efficient computer implementation of the renormalized coupled-cluster methods: The R-CCSD[T], R-CCSD(T), CR-CCSD[T], and CR-CCSD(T) approaches journal December 2002
General atomic and molecular electronic structure system journal November 1993
Advances in electronic structure theory book January 2005
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
The balance between theoretical method and basis set quality: A systematic study of equilibrium geometries, dipole moments, harmonic vibrational frequencies, and infrared intensities journal July 1993
The Theoretical Prediction of Molecular Radical Species:  a Systematic Study of Equilibrium Geometries and Harmonic Vibrational Frequencies journal October 2001
Ultraviolet photoelectron spectrum of nitrite anion journal September 1988
Combining active-space coupled-cluster methods with moment energy corrections via the CC( P ; Q ) methodology, with benchmark calculations for biradical transition states journal April 2012
Merging Active-Space and Renormalized Coupled-Cluster Methods via the CC( P ; Q ) Formalism, with Benchmark Calculations for Singlet–Triplet Gaps in Biradical Systems journal September 2012

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
1
2
3
4-cyclobutanetetraone
coupled-cluster theory
multi-reference configuration interaction
singlet–triplet gap
electronic excitations