Heavy atom compounds represent a challenge for computational chemistry due to the need for simultaneous treatment of relativistic and correlation effects. Often such systems also exhibit strong correlation, which hampers the application of perturbation theory or single-reference coupled cluster (CC) methods. As a viable alternative, we have proposed externally correcting the CC method using the density matrix renormalization group (DMRG) wave functions, yielding the DMRG-tailored CC method. In a previous paper [J. Chem. Phys. 2020, 152, 174107], we reported a first implementation of this method in the relativistic context, which was restricted to molecules with real double group symmetry. In this work, we present a fully general implementation of the method, covering complex and quaternion double groups as well. The 4c-TCC method thus becomes applicable to polyatomic molecules, including heavy atoms. For the assessment of the method, we performed calculations of the chiral uranium compound NUHFI, which was previously studied in the context of the enhancement of parity violation effects. In particular, we performed calculations of a cut of the potential energy surface of this molecule along the stretching of the N-U bond, where the system exhibits strong multireference character. Since there are no experimental data for NUHFI, we have performed also an analogous study of the (more symmetric) NUF3 molecule, where the vibrational frequency of the N-U bond can be compared with spectroscopic data.

Department of Chemistry and Pharmaceutical Sciences De Boelelaan 1108 Vrije Universiteit Amsterdam NL 1081 HZ Amsterdam Netherlands

Department of Mathematics Technical University of Munich Boltzmannstr 3 85748 Garching Germany

Faculty of Mathematics and Physics Charles University Ke Karlovu 3 12116 Prague Czech Republic

Faculty of Science Humanities and Education Technical University of Liberec Studentská 1402 2 461 17 Liberec Czech Republic

Institute for Advanced Study Technical University of Munich Lichtenbergstrasse 2a 85748 Garching Germany

J Heyrovský Institute of Physical Chemistry Academy of Sciences of the Czech Republic v v i Dolejškova 3 18223 Prague 8 Czech Republic

Middle East Technical University Üniversiteler Mahallesi Dumlupınar Bulvarı No 1 06800 Çankaya Ankara Türkiye

Strongly Correlated Systems Lendület Research Group Wigner Research Centre for Physics Konkoly Thege Miklós út 29 33 H 1121 Budapest Hungary

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