TITLE

Complex-scaled equation-of-motion coupled-cluster method with single and double substitutions for autoionizing excited states: Theory, implementation, and examples

AUTHOR(S)
Bravaya, Ksenia B.; Zuev, Dmitry; Epifanovsky, Evgeny; Krylov, Anna I.
PUB. DATE
March 2013
SOURCE
Journal of Chemical Physics;Mar2013, Vol. 138 Issue 12, p124106
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Theory and implementation of complex-scaled variant of equation-of-motion coupled-cluster method for excitation energies with single and double substitutions (EOM-EE-CCSD) is presented. The complex-scaling formalism extends the EOM-EE-CCSD model to resonance states, i.e., excited states that are metastable with respect to electron ejection. The method is applied to Feshbach resonances in atomic systems (He, H-, and Be). The dependence of the results on one-electron basis set is quantified and analyzed. Energy decomposition and wave function analysis reveal that the origin of the dependence is in electron correlation, which is essential for the lifetime of Feshbach resonances. It is found that one-electron basis should be sufficiently flexible to describe radial and angular electron correlation in a balanced fashion and at different values of the scaling parameter, θ. Standard basis sets that are optimized for not-complex-scaled calculations (θ = 0) are not sufficiently flexible to describe the θ-dependence of the wave functions even when heavily augmented by additional sets.
ACCESSION #
86446775

 

Related Articles

  • Effects of electron correlation in the calculation of nuclear magnetic resonance chemical shifts. Gauss, Jürgen // Journal of Chemical Physics;9/1/1993, Vol. 99 Issue 5, p3629 

    Using second-order many-body perturbation theory [MBPT(2)] and the gauge-including atomic orbital (GIAO) ansatz, electron correlation effects are investigated in the calculation of NMR chemical shieldings and shifts. A thorough discussion of the theory, aspects of the implementation as well as...

  • The open shell single reference size-consistent self-consistent singles and doubles configuration interaction method: Application to ionization potentials. Pitarch-Ruiz, J.; Sánchez-Marín, J.; Maynau, D. // Journal of Chemical Physics;1/22/2000, Vol. 112 Issue 4 

    In previous works, the size-consistent self-consistent matrix dressing method has been applied to single reference as well as to complete active space singles and doubles configuration interaction. The wave function of the dressed state was assumed to be dominated by a closed shell determinant....

  • Hypermagnetizability anisotropy (Cotton–Mouton effect) for H2 and D2. Bishop, David M.; Cybulski, Sl\awomir M.; Pipin, Janusz // Journal of Chemical Physics;5/15/1991, Vol. 94 Issue 10, p6686 

    Explicitly electron-correlated wave functions have been used to calculate the hypermagnetizability anisotropy (Δη) for H2 and D2. This property is the essential feature of the birefringence of a material in the presence of a magnetic field (the Cotton–Mouton effect). The...

  • Natural bond orbitals in multiconfigurational expansions: Local treatment of electron correlation in molecules. Nemukhin, A. V.; Weinhold, F. // Journal of Chemical Physics;7/15/1992, Vol. 97 Issue 2, p1095 

    We describe a localized treatment of electron correlation in terms of complete active-space wave functions derived from natural bond orbitals, closely related to the localized transferable units of molecular structure. We find that in many cases the procedure leads to solutions which retain the...

  • Molecular geometry and vibrational frequencies of ozone from compact variational wave functions... Leininger, Matthew L.; Schaefer III, Henry F. // Journal of Chemical Physics;12/1/1997, Vol. 107 Issue 21, p9059 

    Compares the performance of the multireference configuration interaction singles and doubles (CISD) method to that of other approaches which include a large degree of electron correlation. References chosen by the method as references for substitutions within an active orbital space; CISD wave...

  • The effect of spin-orbit coupling on the magnetic properties of H[sub 2]Ti(mu-H)[sub 2]TiH[sub 2]. Webb, Simon P.; Gordon, Mark S. // Journal of Chemical Physics;7/15/1998, Vol. 109 Issue 3, p919 

    Investigates the excited states of singlet and triplet H[sub 2]Ti(mu-H)[sub 2]TiH[sub 2] using multiconfigurational wave functions. Optimization of orbitals to determine the orbital relaxation effects; Impact of electron correlation on excited state relative energies; Introduction of spin-orbit...

  • An ab initio SCF-CI study of anharmonic vibrational effects in the HCO–HOC radical pair. Pauzat, F.; Chekir, S.; Ellinger, Y. // Journal of Chemical Physics;9/1/1986, Vol. 85 Issue 5, p2861 

    We report the results of a series of SCF-CI calculations on the ground state of the HCO–HOC radical pair. The calculations have focused on an accurate determination of the geometries, force constants, and anharmonic effects; special attention has been devoted to the role of these effects...

  • 5f band dispersion in the highly correlated electronic structure of uranium compounds. Moore, D. P.; Joyce, J. J.; Arko, A. J.; Morales, L.; Sarrao, J. // AIP Conference Proceedings;2000, Vol. 532 Issue 1, p420 

    Despite the fact that the 5f shell of the light actinides is less than half filled, the relatively short radial extent of 5f-electron wave functions yields at most minimal f-f overlap (the critical actinide-actinide spacing for which f-f overlap is no longer viable was first quantified by H....

  • Higher-order polarizabilities for the helium isoelectronic series. Bishop, David M.; Rérat, Michel // Journal of Chemical Physics;11/1/1989, Vol. 91 Issue 9, p5489 

    Accurate and explicitly electron-correlated wave functions have been used to calculate the dipole polarizability (α), second hyperpolarizability (γ), dipole–dipole–quadrupole (B), and quadrupole–quadrupole (C) polarizabilities of the helium isoelectronic series...

Share

Read the Article

Courtesy of VIRGINIA BEACH PUBLIC LIBRARY AND SYSTEM

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics