We present a four-component relativistic unitary coupled cluster method for atoms and molecules. We have used commutator-based non-perturbative approximation using the "Bernoulli expansion" to derive an approximation to the relativistic unitary coupled cluster method. The performance of the full quadratic unitary coupled-cluster singles and doubles method (qUCCSD), as well as a perturbative approximation variant (UCC3), has been reported for both energies and properties. It can be seen that both methods give results comparable to those of the standard relativistic coupled cluster method. The qUCCSD method shows better agreement with experimental results due to the better inclusion of relaxation effects. The relativistic UCC3 and qUCCSD methods can simulate the spin-forbidden transition with easy access to transition properties. A natural spinor-based scheme to reduce the computational cost of relativistic UCC3 and qUCCSD methods has been discussed.

Download full-text PDF

Source
http://dx.doi.org/10.1063/5.0207091DOI Listing

Publication Analysis

Top Keywords

coupled cluster
16
cluster method
16
relativistic unitary
12
unitary coupled
12
four-component relativistic
8
method atoms
8
atoms molecules
8
method quccsd
8
relativistic ucc3
8
ucc3 quccsd
8

Similar Publications

Improving Bond Dissociations of Reactive Machine Learning Potentials through Physics-Constrained Data Augmentation.

J Chem Inf Model

January 2025

Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.

In the field of computational chemistry, predicting bond dissociation energies (BDEs) presents well-known challenges, particularly due to the multireference character of reactive systems. Many chemical reactions involve configurations where single-reference methods fall short, as the electronic structure can significantly change during bond breaking. As generating training data for partially broken bonds is a challenging task, even state-of-the-art reactive machine learning interatomic potentials (MLIPs) often fail to predict reliable BDEs and smooth dissociation curves.

View Article and Find Full Text PDF

Interstellar spectroscopic detection of HC(S)NC and DC(S)NC.

J Chem Phys

January 2025

Department of Earth and Environmental Science, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6243, USA.

The detection of HC(S)CN in TMC-1 suggests that HC(S)NC may also exist. To aid in its possible detection, HC(S)NC and its deuterated isotopologue DC(S)NC were investigated via high-level ab initio methods, specifically CCSD(T) and CCSD(T)-F12. By utilizing multidimensional potential energy surfaces derived from explicitly correlated coupled-cluster calculations, we analyzed their geometrical parameters, vibrational frequencies, rotational constants, and a comprehensive set of spectroscopic constants generated via the vibrational second-order perturbation theory, vibrational self-consistent field, and vibrational configuration interaction theory(VCI) approaches.

View Article and Find Full Text PDF

Core-Excited States for Open-Shell Systems in Similarity-Transformed Equation-of-Motion Theory.

J Chem Theory Comput

January 2025

Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.

X-ray absorption spectroscopy (XAS) is a powerful method for exploring molecular electronic structure by exciting core electrons into higher unoccupied molecular orbitals. In this study, we present the first integration of the spin-unrestricted similarity-transformed equation-of-motion coupled cluster method (CVS-USTEOM-CCSD) for core-excited and core-ionized states into the ORCA quantum chemistry package. Using the core-valence separation (CVS) approach, we evaluate the accuracy of CVS-USTEOM-CCSD across 13 open-shell organic systems, covering over 20 core excitations with diverse spin multiplicities (doublet, triplet, and quartet).

View Article and Find Full Text PDF

Cavitation has been a hot research topic for scholars in various fields because of the intense mechanical, chemical, and thermal effects of bubble collapse. It forms a cluster of bubbles, and the bubbles will affect, interfere with, and couple with each other. To grasp the main factors affecting bubble collapse and the interbubble mechanism, the paper adopts the molecular dynamics simulation combined with the coarse-grained force field to study the collapse process of the double bubble model and takes the dynamic shape change of the bubbles, the local velocity distribution, and the local pressure distribution as the object to summarize the position angle, the shock velocity, and the bubble distance on the collapse law and the primary and secondary influence relationship and then reveals the interbubble mechanism.

View Article and Find Full Text PDF

Background: Adversity in childhood is increasing in the United Kingdom. Complex health and social problems affecting children cluster in families where adults also have high need, but services are rarely aligned to support the whole family. Household level segmentation can help identify households most needing integrated support.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!