Waelz, Gero and Usvyat, Denis and Korona, Tatiana and Schuetz, Martin (2016) A hierarchy of local coupled cluster singles and doubles response methods for ionization potentials. JOURNAL OF CHEMICAL PHYSICS, 144 (8): 084117. ISSN 0021-9606, 1089-7690
Full text not available from this repository. (Request a copy)Abstract
We present a hierarchy of local coupled cluster (CC) linear response (LR) methods to calculate ionization potentials (IPs), i.e., excited states with one electron annihilated relative to a ground state reference. The time-dependent perturbation operator V(t), as well as the operators related to the first-order (with respect to V(t)) amplitudes and multipliers, thus are not number conserving and have half-integer particle rank m. Apart from calculating IPs of neutral molecules, the method offers also the possibility to study ground and excited states of neutral radicals as ionized states of closed-shell anions. It turns out that for comparable accuracy IPs require a higher-order treatment than excitation energies; an IP-CC LR method corresponding to CC2 LR or the algebraic diagrammatic construction scheme through second order performs rather poorly. We therefore systematically extended the order with respect to the fluctuation potential of the IP-CC2 LR Jacobian up to IP-CCSD LR, keeping the excitation space of the first-order (with respect to V(t)) cluster operator restricted to the m = 1/2 circle plus 3/2 subspace and the accuracy of the zero-order (ground-state) amplitudes at the level of CC2 or MP2. For the more expensive diagrams beyond the IP-CC2 LR Jacobian, we employ local approximations. The implemented methods are capable of treating large molecular systems with hundred atoms or more. (C) 2016 AIP Publishing LLC.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | THE-IDENTITY APPROXIMATION; EXCITED-STATES; MODEL CC2; POLARIZATION PROPAGATOR; ELECTRON CORRELATION; LARGE MOLECULES; IONIZED STATES; BASIS-SETS; 1ST-ORDER PROPERTIES; EXCITATION-ENERGIES; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Mar 2019 07:30 |
| Last Modified: | 12 Mar 2019 07:30 |
| URI: | https://pred.uni-regensburg.de/id/eprint/2385 |
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