TY - JOUR

T1 - Vibrational Embedding Theory

AU - Hellmers, Janine Isabel

AU - König, Carolin

N1 - This work has been supported by the Deutsche Forschungsgemeinschaft (DFG) through the Emmy Noether Young Group Leader Programme (Project No. KO 5423/1-1). We thank Ove Christiansen for insightful discussions and are grateful to Kiyoshi Yagi for the potential energy surfaces for the water clusters including that of the bacteriorhodopsin cluster and the PDB file for the visualization of the bacteriorhodopsin water cluster. The computations were carried out on the cluster system at the Leibniz University Hannover, Germany, which was funded by the Leibniz University Hannover, the Lower Saxony Ministry of Science and Culture (MWK) and the DFG.

PY - 2023/9/14

Y1 - 2023/9/14

N2 - We suggest a consistent framework for the embedding of reduced-space correlated vibrational wave functions in a potential of the remaining modes and generalize this concept to arbitrary many subspaces. We present an implementation of this framework for vibrational coupled-cluster theory and response treatments. For C=O stretches of small molecules, we show that the embedded treatment accelerates convergence for enlarging subsets. For the water dimer and trimer as well as a water wire in bacteriorhodopsin, we investigate different partitioning schemes for the embedding approach: In the local partitioning of the vibrations, the modes dominated by motions in the same spatial region are correlated, whereas in the energy-based partitioning, modes of similar fundamental frequencies are correlated. In most cases, we obtain better agreement with superset reference results for the local partitioning than for energy-based partitioning. This work represents an important step toward multi-level methodologies in vibrational-structure theory required for its application to sizable (bio-)molecular systems.

AB - We suggest a consistent framework for the embedding of reduced-space correlated vibrational wave functions in a potential of the remaining modes and generalize this concept to arbitrary many subspaces. We present an implementation of this framework for vibrational coupled-cluster theory and response treatments. For C=O stretches of small molecules, we show that the embedded treatment accelerates convergence for enlarging subsets. For the water dimer and trimer as well as a water wire in bacteriorhodopsin, we investigate different partitioning schemes for the embedding approach: In the local partitioning of the vibrations, the modes dominated by motions in the same spatial region are correlated, whereas in the energy-based partitioning, modes of similar fundamental frequencies are correlated. In most cases, we obtain better agreement with superset reference results for the local partitioning than for energy-based partitioning. This work represents an important step toward multi-level methodologies in vibrational-structure theory required for its application to sizable (bio-)molecular systems.

UR - http://www.scopus.com/inward/record.url?scp=85170631682&partnerID=8YFLogxK

U2 - 10.1063/5.0155983

DO - 10.1063/5.0155983

M3 - Article

VL - 159

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 10

M1 - 104108

ER -