Real-valued continuum remover potential: An improved L2-stabilization method for the chemistry of electronic resonance states

Sajeev, Y.

doi:10.1016/j.cplett.2013.09.052

Cited by 24 publications

(43 citation statements)

References 47 publications

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“…Several approaches have been proposed for the computation of resonances. The list comprises artificial stabilizing potentials, [28][29][30][31] stabilization methods, 32,33 complex scaling, [34][35][36][37][38] exterior complex scaling, 39,40 complex basis functions, 41,42 and complex absorbing potentials (CAPs). [43][44][45][46][47][48] Here, we employ the CAP approach, where an imaginary potential is added to the Hamiltonian in order to describe the resonance as an L 2 -integrable discrete state.…”

Section: Introductionmentioning

confidence: 99%

Characterizing metastable states beyond energies and lifetimes: Dyson orbitals and transition dipole moments

Jagau

Krylov

2016

The Journal of Chemical Physics

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The theoretical description of electronic resonances is extended beyond calculations of energies and lifetimes. We present the formalism for calculating Dyson orbitals and transition dipole moments within the equation-of-motion coupled-cluster singles and doubles method for electron-attached states augmented by a complex absorbing potential (CAP-EOM-EA-CCSD). The capabilities of the new methodology are illustrated by calculations of Dyson orbitals of various transient anions. We also present calculations of transition dipole moments between transient and stable anionic states as well as between different transient states. Dyson orbitals characterize the differences between the initial neutral and final electron-attached states without invoking the mean-field approximation. By extending the molecular-orbital description to correlated many-electron wave functions, they deliver qualitative insights into the character of resonance states. Dyson orbitals and transition moments are also needed for calculating experimental observables such as spectra and cross sections. Physically meaningful results for those quantities are obtained only in the framework of non-Hermitian quantum mechanics, e.g., in the presence of a complex absorbing potential (CAP), when studying resonances. We investigate the dependence of Dyson orbitals and transition moments on the CAP strength and illustrate how Dyson orbitals help understand the properties of metastable species and how they are affected by replacing the usual scalar product by the so-called c-product.

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Section: Introductionmentioning

confidence: 99%

Characterizing metastable states beyond energies and lifetimes: Dyson orbitals and transition dipole moments

Jagau

Krylov

2016

The Journal of Chemical Physics

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“…The details of this approach can be found in our previous publications (see Refs. [20][21][22] and the essential details pertaining to the computational results given in this communication are included in the supplementary material.…”

Section: Anti−bonding Chmentioning

confidence: 99%

“…19 The existing many-electron ab initio quantum chemical methods offer a good route to solve the bound state like discrete eigen solutions of the analytically continued Hamiltonian. 20 Here, we have used continuum remover potential [20][21][22] within the framework of the equation-of-motion coupled cluster method as the analytically continued ab initio many-electron analytical method. The details of this approach can be found in our previous publications (see Refs.…”

Section: Anti−bonding Chmentioning

confidence: 99%

Communication: Low-energy free-electron driven molecular engineering: In situ preparation of intrinsically short-lived carbon-carbon covalent dimer of CO

Davis

Sajeev

2017

The Journal of Chemical Physics

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Molecular modification induced through the resonant attachment of a low energy electron (LEE) is a novel approach for molecular engineering. In this communication, we explore the possibility to use the LEE as a quantum tool for the in situ preparation of short lived molecules. Using ab initio quantum chemical methods, this possibility is best illustrated for the in situ preparation of the intrinsically short-lived carbon-carbon covalent dimer of CO from a glyoxal molecule. The chemical conversion of glyoxal to the covalent dimer of CO is initiated and driven by the resonant capture of a near 11 eV electron by the glyoxal molecule. The resulting two-particle one-hole (2p-1h) negative ion resonant state (NIRS) of the glyoxal molecule undergoes a barrierless radical dehydrogenation reaction and produces the covalent dimer of CO. The autoionization electron spectra from the 2p-1h NIRS at the dissociation limit of the dehydrogenation reaction provides access to the electronic states of the CO dimer. The overall process is an example of a catalytic electron reaction channel.

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“…These states are autoionizing states and can not be converged using standard ab inito methods. 10 However, for poly-atomic molecules, a large number of doubly excited or even multiply excited closed-shell configurations are possible below the first ionization threshold. Unlike in the diatomic molecules, the main advantage of large molecule is that the virtual orbitals that are localized on different atoms other than the atoms constituting the fragmentation coordinate can be chosen for the double occupancy.…”

Section: Numerical Testsmentioning

confidence: 99%

EOMCC over excited state Hartree-Fock solutions (ESHF-EOMCC): An efficient approach for the entire ground state potential energy curves of higher-order bonds

Sajeev

2015

AIP Advances

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The equation-of-motion coupled cluster (EOMCC) method based on the excited state Hartree-Fock (ESHF) solutions is shown to be appropriate for computing the entire ground state potential energy curves of strongly correlated higher-order bonds. The new approach is best illustrated for the homolytic dissociation of higher-order bonds in molecules. The required multireference character of the true ground state wavefunction is introduced through the linear excitation operator of the EOMCC method. Even at the singles and doubles level of cluster excitation truncation, the nonparallelity error of the ground state potential energy curve from the ESHF based EOMCC method is small. C 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License. [http://dx

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Real-valued continuum remover potential: An improved L2-stabilization method for the chemistry of electronic resonance states

Cited by 24 publications

References 47 publications

Characterizing metastable states beyond energies and lifetimes: Dyson orbitals and transition dipole moments

Characterizing metastable states beyond energies and lifetimes: Dyson orbitals and transition dipole moments

Communication: Low-energy free-electron driven molecular engineering: In situ preparation of intrinsically short-lived carbon-carbon covalent dimer of CO

EOMCC over excited state Hartree-Fock solutions (ESHF-EOMCC): An efficient approach for the entire ground state potential energy curves of higher-order bonds

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