The numerous existing publications on benchmarking quantum chemistry methods for excited states rarely include Charge Transfer (CT) states, although many interesting phenomena in, e.g., biochemistry and material physics involve the transfer of electrons between fragments of the system. Therefore, it is timely to test the accuracy of quantum chemical methods for CT states, as well. In this study we first propose a new benchmark set consisting of dimers having low-energy CT states. On this set, the vertical excitation energy has been calculated with Coupled Cluster methods including triple excitations (CC3, CCSDT-3, CCSD(T)(a)*), as well as with methods including full or approximate doubles (CCSD, STEOM-CCSD, CC2, ADC(2), EOM-CCSD(2)). The results show that the popular CC2 and ADC(2) methods are much less accurate for CT states than for valence states. On the other hand, EOM-CCSD seems to have similar systematic overestimation of the excitation energies for both types of states. Among the triples methods the novel EOM-CCSD(T)(a)* method including noniterative triple excitations is found to stand out with its consistently good performance for all types of states, delivering essentially EOM-CCSDT quality results.

In this paper the potential energy curves of CT states and their interaction with local ones have been investigated. Besides the global view of these curves, special attention has been paid to the region of the crossing and the infinite separation limit. It was found that triple excitations are needed to accurately describe potential energy surfaces of CT states. Among the cheaper variants, both STEOM-CCSD and CCSD(T)(a)* methods are promising in this respect. The somewhat larger error of CCSD for CT states can be explained by its size extensivity error and the overestimation of the asymptotic excitation energy. Second order approximations are not advantageous for the error cancellation, in fact CC2 is much worse for CT states than any other method investigated here. The results also show that the location of the (avoided) crossings of local and CT states depend very much on the accurate description of the CT states. Failure to describe this topology might affect dynamics, and a warning, in particular in case of CC2, should be issued if CT states play a role in the physics of the problem.

There are numerous publications on benchmarking quantum chemistry methods for excited states. These studies rarely include Charge Transfer (CT) states although many interesting phenomena in e.g. biochemistry and material physics involve transfer of electron between fragments of the system. Therefore, it is timely to test the accuracy of quantum chemical methods for CT states, as well. In this study we first suggest a set benchmark systems consisting of dimers having low-energy CT states. On this set, the excitation energy has been calculated with coupled cluster methods including triple excitations (CC3, CCSDT-3, CCSD(T)(a)* ), as well as with methods including full or approximate doubles (CCSD, STEOM-CCSD, CC2, ADC(2), EOM-CCSD(2)). The results show that the popular CC2 and ADC(2) methods are much more inaccurate for CT states than for valence states. On the other hand, CCSD seems to have similar systematic overestimation of the excitation energies for both valence and CT states. Concerning triples methods, the new CCSD(T)(a)* method including non-iterative triple excitations preforms very well for all type of states, delivering essentially CCSDT quality results.<br>

The molecular level understanding of electronic transport properties depends on the reliable theoretical description of charge-transfer (CT)-type electronic states. In this paper, the performance of spin-component-scaled variants of the popular CC2 and ADC(2) methods is evaluated for CT states, following benchmark strategies of earlier studies that revealed a compromised accuracy of the unmodified models. In addition to statistics on the accuracy of vertical excitation energies at equilibrium and infinite separation of bimolecular complexes, potential energy surfaces of the ammonia−fluorine complex are also reported. The results show the capability of spin-component-scaled approaches to reduce the large errors of their regular counterparts to a significant extent, outperforming even the coupled-cluster single and double method in many cases. The cost-effective scaled-opposite-spin variants are found to provide a remarkably good agreement with the CCSDT-3 reference data, thereby being recommended methods of choice in the study of charge-transfer states.

Es werden mat der yon P. Gomb~s entwickelten Ngherungsmethode:) die 3 S-, 4S-, 3P-, 4P-, 3D-Terme des Na-Atoms, die 4S-, 4P-, 3D-, 4F-, 5 G-Terme des K-Atoms und der Grundterm der AI+-und A1 + +-Ionen mit den entsprechenden Eigenfunktionen bereehnet. Die Resultate, welehe mit den empirischen gut fibereinstimmen, werden diskutiert.Es wird die yon P. Gomb~s zur Bestimmung der Terme und Eigenfunktionen entwickelte N~herungsmethode:) auf die Atome und Ionen Na, K, A1 + und A1 ++ angewendet. Beziiglich der Methode verweisen ~ir auf die Arbeit yon P.