Multireference Rayleigh-Schrödinger perturbation theory and its application.

Based on the complete active space multireference wavefunction, multireference Rayleigh-Schrödinger perturbation theory (MRSPT) is derived with the assumption that the orbital energies of active orbitals are the same as ε¯, an unknown parameter. In this work, ε¯ is optimized at the MRSPT2 level. The second and third order perturbation theories are shown numerically to be size extensive. The second order perturbation theory is exploited to compute the ground state energies of F2, AlH, HCl, and P2 and to optimize the equilibrium bond lengths and harmonic vibrational frequencies of BH, BF, P2, HF, and F2. The dissociation behaviors of NH3 and OH- have also been investigated. Comparisons with other theoretical models as well as the experimental data have been made to show advantages of the present theory.

• Publication year

  2019

• Venue

  Journal of Chemical Physics

• Publication date

  2019-03-28

• Fields of study

  Medicine, Physics, Chemistry

• Identifiers
  DOI 10.1063/1.5081814PMID 30927868
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Application of multireference linearized coupled-cluster theory to atomic and molecular systems

  2018cited by this paper
• Multireference Approaches for Excited States of Molecules.

  2018cited by this paper
• Fitting and Extrapolation of Configuration Interaction Energies in Complete Active Space

  2017cited by this paper
• Multireference Perturbation Theory and Multireference Coupled Cluster Theory Based on the "Block-Correlation" Framework

  2017cited by this paper
• Relationship between the Bond Dipole Moment and Bond Angle of Polar Molecules

  2016cited by this paper
• Computation of Electron Affinities with the Second Order Multireference Perturbation Theory

  2015cited by this paper
• State‐specific multireference perturbation theory with improved virtual orbitals: Taming the ground state of F2, Be2, and N2

  2015cited by this paper
• A new size extensive multireference perturbation theory

  2014cited by this paper
• Nonorthogonal orbital based n-body reduced density matrices and their applications to valence bond theory. III. Second-order perturbation theory using valence bond self-consistent field function as reference.

  2014cited by this paper
• The relative energies of polypeptide conformers predicted by linear scaling second-order Møller-Plesset perturbation theory

  2014cited by this paper
• Block correlated second order perturbation theory with a generalized valence bond reference function.

  2013cited by this paper
• Multiconfiguration self-consistent field and multireference configuration interaction methods and applications.

  2012cited by this paper
• A spin-adapted size-extensive state-specific multi-reference perturbation theory. I. Formal developments.

  2012cited by this paper
• Orbitally invariant internally contracted multireference unitary coupled cluster theory and its perturbative approximation: theory and test calculations of second order approximation.

  2012cited by this paper
• New implementation of the configuration-based multi-reference second order perturbation theory.

  2012cited by this paper
• On the performance of the open-shell perturbation theory

  2011cited by this paper
• Extended multi-configuration quasi-degenerate perturbation theory: the new approach to multi-state multi-reference perturbation theory.

  2011cited by this paper
• Study of the Ground State Dissociation of Diatomic Molecular Systems Using State-Specific Multireference Perturbation Theory: A Brillouin-Wigner Scheme.

  2010cited by this paper
• Configuration-driven unitary group approach for generalized Van Vleck variant multireference perturbation theory.

  2009cited by this paper
• A companion perturbation theory for state-specific multireference coupled cluster methods.

  2009cited by this paper
• A Single Reference Perturbation Theory beyond the Møller-Plesset Partition.

  2009cited by this paper
• Theoretical study on the size consistency of the second and third order energies of the multireference perturbation theory

  2007cited by this paper
• Numerical Study on the Size Consistency of the Multireference Perturbation Theory

  2007cited by this paper
• Multiconfiguration perturbation theory: size consistency at second order.

  2005cited by this paper
• Multireference perturbation theory with optimized partitioning. I. Theoretical and computational aspects

  2003cited by this paper
• On the perturbation of multiconfiguration wave functions

  2003cited by this paper
• Two-body zeroth order hamiltonians in multireference perturbation theory: The APSG reference state

  2002cited by this paper
• Explication and revision of generalized Van Vleck perturbation theory for molecular electronic structure

  2002cited by this paper
• New time‐independent perturbation theory for the multireference problem

  2002cited by this paper
• Introduction of n-electron valence states for multireference perturbation theory

  2001cited by this paper
• Electronic, Structural, and Hyperfine Interaction Investigations on Rydberg Molecules: NH4, OH3, and FH2

  2001cited by this paper
• Multireference Møller–Plesset method with a complete active space configuration interaction reference function

  2001cited by this paper
• Property calculations using perturbed orbitals via state-specific multireference coupled-cluster and perturbation theories

  1999cited by this paper
• Molecular Applications of a Size-Consistent State-Specific Multireference Perturbation Theory with Relaxed Model-Space Coefficients.

  1999cited by this paper
• Development of a size-consistent state-specific multireference perturbation theory with relaxed model-space coefficients

  1999cited by this paper
• The reduced model space method in multireference second-order perturbation theory

  1998cited by this paper
• Canonical Van Vleck Quasidegenerate Perturbation Theory with Trigonometric Variables

  1996cited by this paper
• Computational methods in quantum chemistry

  1996cited by this paper
• Third-order multireference perturbation theory The CASPT3 method

  1996cited by this paper
• The choice of a zeroth-order Hamiltonian for second-order perturbation theory with a complete active space self-consistent-field reference function

  1995cited by this paper
• Considerations in constructing a multireference second‐order perturbation theory

  1994cited by this paper
• Construction of open shell perturbation theory invariant with respect to orbital degeneracy

  1994cited by this paper
• General atomic and molecular electronic structure system

  1993cited by this paper
• Quasidegenerate perturbation theory with multiconfigurational self‐consistent‐field reference functions

  1993cited by this paper
• Second-order perturbation theory with a complete active space self-consistent field reference function

  1992cited by this paper
• Multireference Møller-Plesset method

  1992cited by this paper
• Molecular Spectra and Molecular Structure

  1992cited by this paper
• Perturbation theory for open shell systems

  1991cited by this paper
• Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen

  1989cited by this paper
• Analysis of abinitio effective valence shell Hamiltonian calculations using third order quasidegenerate many‐body perturbation theory

  1981cited by this paper
• Generalized perturbation theory of effective valence shell hamiltonians

  1979cited by this paper
• The influence of polarization functions on molecular orbital hydrogenation energies

  1973cited by this paper
• Note on an Approximation Treatment for Many-Electron Systems

  1934cited by this paper

• PASPT2: A Size-Extensive and Size-Consistent Partial-Active-Space Multistate Multireference Second-Order Perturbation Theory for Strongly Correlated Electrons

  2026cites this paper
• Block effective Hamiltonian theory and its application to atomic and molecular systems

  2025cites this paper
• Theoretical Study on the Properties of Small Molecules with the Block Effective Hamiltonian Theory and Multireference Methods.

  2025cites this paper
• Calculations of atomisation energy and singlet–triplet gap with iterative multireference configuration interaction

  2022cites this paper
• Block Effective Hamiltonian Theory and Its Application.

  2022cites this paper
• Taming the excited states of butadiene, hexatriene, and octatetraene using state specific multireference perturbation theory with density functional theory orbitals.

  2020cites this paper
• Investigation of Multiple Bond Dissociation Using Brillouin-Wigner Perturbation with Improved Virtual Orbitals.

  2020cites this paper
• Theoretical study on divergence problems of single reference perturbation theories

  2019cites this paper
• Simplified Treatment of Electronic Structures of the Lowest Singlet and Triplet States of Didehydropyrazines.

  2019cites this paper