Perturbative triples correction for the equation-of-motion coupled-cluster wave functions with single and double substitutions for ionized states: Theory, implementation, and examples

Manohar, Prashant U.; Stanton, John F.; Krylov, Anna I.

doi:doi:10.1063/1.3231133

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Non-Markovian theory for the waiting time distributions of single electron transfers

We derive a non-Markovian theory for waiting time distributions of consecutive single electron transfer events. The presented microscopic Pauli rate equation formalism couples the open electrodes to the many-body system, allowing to take finite bias and temperature into consideration. Numerical results reveal transient oscillations of distinct system frequencies due to memory in the waiting time distributions. Memory effects can be approximated by an expansion in non-Markovian corrections. This...

Full-electron calculation of effective electronic couplings and excitation energies of charge transfer states: Application to hole transfer in DNA π-stacks

In this work I develop and apply a theoretical method for calculating effective electronic couplings (or transfer integrals) between redox sites involved in hole or electron transfer reactions. The resulting methodology is a refinement and a generalization of a recently developed approach for transfer integral evaluation. In fact, it holds for any overlap between the charge-localized states used to represent charge transfer (CT) processes in the two-state model. The presented theoretical and co...

A noniterative N⁶ triples energy correction is presented for the equation-of-motion coupled-cluster method with single and double substitutions for ionized states (EOM-IP-CCSD). The correction, which is size intensive, is derived using a second-order Rayleigh–Schrödinger perturbative treatment and is similar to the approach of Stanton and Gauss [Theor. Chim. Acta 93, 303 (1996)] . In the present implementation, only the target EOM-IP states are corrected, and the reference state is described by CCSD; the method is therefore more useful for the study of the target states themselves than ionization potentials. The performance of the correction, which demonstrates the caveat above, is demonstrated by applications to singlet methylene, BNB⁻, nitrogen, carbon monoxide, acetylene, benzene, thymine, and adenine.

Article Outline

INTRODUCTION
THEORY
RESULTS AND DISCUSSION
1. Computational details
2. Methylene
3. BNB
4. Nitrogen, carbon monoxide, and acetylene
5. Benzene
6. Thymine
7. Adenine
CONCLUSIONS

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KEYWORDS and PACS

Keywords

boron compounds, carbon compounds, coupled cluster calculations, ionisation potential, negative ions, nitrogen, organic compounds, perturbation theory

PACS

31.15.bw

Coupled-cluster theory
33.15.Ry

Ionization potentials, electron affinities, molecular core binding energy
31.15.xp

Perturbation theory

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http://link.aip.org/link/doi/10.1063/1.3231133

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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