Spin-adaptation of virtual functions in state-specific multireference perturbation theory is examined. Redundancy occurring among virtual functions generated by unitary group based excitation operators on a model-space function is handled by canonical orthogonalization. The treatment is found to remove non-physical kinks observed earlier on potential energy surfaces. Sensitivity analysis of the new approach confirms the elimination of the drastic increase in singular values of sensitivity matrices, reported earlier.
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http://dx.doi.org/10.1063/1.4795436 | DOI Listing |
J Chem Phys
November 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata Nadia, Mohanpur 741246, West Bengal, India.
In this paper, we investigate the role of electron correlation in predicting the S1-S0 and T1-S0 excitation energies and, hence, the singlet-triplet gap (ΔEST) in a set of cyclazines, which act as templates for potential candidates for fifth generation organic light emitting diode materials. This issue has recently garnered much interest with the focus being on the inversion of the ΔEST, although experiments have indicated near degenerate levels with both positive and negative being within the experimental error bar [J. Am.
View Article and Find Full Text PDFJ Phys Chem Lett
July 2024
Algorithmiq Ltd., Kanavakatu 3C, FI-00160 Helsinki, Finland.
Quantum chemistry simulations offer a cost-effective way to computationally design BODIPY photosensitizers. However, accurate predictions of excitation energies pose a challenge for time-dependent density functional theory and equation-of-motion coupled-cluster singles and doubles methods. By contrast, reliable predictions can be achieved by multireference quantum chemistry methods; unfortunately, their computational cost increases exponentially with the number of electrons.
View Article and Find Full Text PDFJ Chem Theory Comput
May 2024
Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, 31000 Toulouse, France.
We reexamine ΔCCSD, a state-specific coupled-cluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient when dealing with doubly excited states, a domain in which the standard equation-of-motion CCSD (EOM-CCSD) formalism falls short. Our goal here to evaluate the effectiveness of ΔCCSD when applied to other types of excited states, comparing its consistency and accuracy with EOM-CCSD.
View Article and Find Full Text PDFJ Chem Phys
December 2023
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Dolejškova 3, 18223 Prague 8, Czech Republic.
In the past decade, the quantum chemical version of the density matrix renormalization group method has established itself as the method of choice for strongly correlated molecular systems. However, despite its favorable scaling, in practice, it is not suitable for computations of dynamic correlation. Several approaches to include that in post-DMRG methods exist; in our group, we focused on the tailored coupled cluster (TCC) approach.
View Article and Find Full Text PDFJ Chem Phys
October 2023
Centre for Quantum Engineering, Research, and Education (CQuERE), TCG CREST, Kolkata, India.
The Unitary Group Adaptation (UGA) offers a very compact and efficient spin adaptation strategy for any spin-free Hamiltonian in a many body framework. Our use of UGA in the context of state-specific (SS) Jeziorski-Monkhorst Ansatz based multireference coupled cluster (MRCC) theory obviates the non-commutativity between the spin-free cluster operators via a normal ordered exponential parametrization in the wave operator. A previous formulation of UGA-SSMRCC by us [R.
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