Search arXiv⌕ Search
Home/Archive/arXiv

arXiv · 2110.00572

Relativistic and magnetic Breit effects for the isomerization of Sg(CO)6 and Sg(OC)6

G. L. Malli·W. Loveland
View original source ↗Read source document ↗Export metadata ↓

Abstract

Abstract Our ab initio all-electron relativistic Dirac-Fock (DF) calculations for seaborgium hexacarbonyl Sg(CO)6 and seaborgium hexaisocarbonyl Sg(OC)6 predict atomization energies of 68.80 and 64.30 eV. Our Dirac-Fock-Breit-Gaunt (DFBG) calculations for Sg(CO)6 and Sg(OC)6 yield atomization energies of 69.18 and 64.77 eV. However, our calculated non-relativistic (NR) Ae for Sg (CO)6 and Sg(OC)6 are 68.46 and 62.62 eV. The calculated isomerization energies at the DFBG, DF, and NR levels are 4.41,4.50 and 5.83 eV. The contribution of relativity to the Eiso is - ~1.33 eV. The optimized bond distances Sg-C and C-O for octahedral Sg(CO)6 using our DF (NR) calculations are 2.151 ( 2.318 and 1.119 ( 1.114 (ang}). The optimized six Sg-O and C-O bond distances for octahedral Sg(OC)6 at the DF level are equal to 4.897 and 1.108 {ang}. However, the optimized four Sg-O bond distances for the octahedral Sg(OC)6 at the NR level are 5.160 {ang} each, and two Sg-O bonds of 2.721 {ang} each, but all six C-O bonds are 1.108{ang} each. The energies at the DF level of theory for the reaction Sg+6CO to yield Sg (CO)6 and Sg(OC)6 are calculated as -7.30 and -2.80 eV. Moreover, the energies of the reaction at the DFBG level to yield Sg(CO)6 and Sg(OC)6 are very close to those predicted at the DF level of theory of -7.17 and -2.76 eV. However, the NR energies of the above-mentioned reaction are -6.99 and -1.15 eV. The mean bond energies predicted for Sg(CO)6 with our DF, DFBG, and NR calculations are 117.40 , 115.31, and 112.41 kJ/mol, whereas the mean bond energies calculated for the isomer Sg(OC)6 at DF, DFBG and NR levels are 45.03 ,44.39 and 18.49 kJ/mole. The predicted existence of both the isomers with Eiso of ~ 4.50 and ~ 5.80 eV, may cause problems for experimental identification of seaborgium hexacarbonyl.

Explore related subjects

physics.chem-ph

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

G. L. Malli, W. Loveland. 2022-06-07. Relativistic and magnetic Breit effects for the isomerization of Sg(CO)6 and Sg(OC)6. https://arxiv.org/abs/2110.00572

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

arXiv2026

Charge Transfer with a Spin. I: A Variational Constrained-CASSCF Framework for Investigating Charge Transfer in the Presence of Spin-Orbit Coupling

Charge transfer in open-shell molecular systems can involve a delicate interplay between charge localization, orbital relaxation, and spin-orbit coupling (SOC), particularly near ground-excited state crossings. Here, we introduce a very inexpensive variational framework for treating these effects in odd-electron systems by extending the electron/hole-transfer Dynamically-weighted State-Averaged Constrained CASSCF (eDSC/hDSC) method to include SOC. Our method incorporates the SOC Hamiltonian directly into the variational orbital optimization through complex-valued spinor orbitals, allowing orbital and spin degrees of freedom to relax self-consistently while preserving the time-reversal symmetry of doublet states. The method achieves smooth potential energy surfaces and rapid self-consistent field (SCF) convergence; moreover, from physically small to artificially large SOC strengths, the calculation can be converged to very tight thresholds across the whole potential energy surface. While the results presented here are for systems with two charge centers, as shown in the appendix, the theory is quite general and can be adapted to either a system of $N$ charge centers or a metal-molecule surface with a continuum of states, so that charge transport (and not just charge transfer) can also be studied. The approach therefore provides a route towards ab initio studies of spin-dependent charge transfer and charge transport in molecular systems with nontrivial spin degrees of freedom.

physics.chem-ph↗
arXiv2026

Charge Transfer with a Spin. II: A Framework for Diabatization which Localizes Charge and Spin

We investigate a diabatization procedure that localizes charges (in real space) and localizes spins (in spin space) for open-shell systems that exhibit charge transfer in the presence of spin-orbit coupling. The procedure is applied to a two-state crossing between pairs of Kramers-restricted doublet states (which can also be considered effectively a four-state crossing). To generate the relevant diabatic states, we employ a two-step optimization over complex-unitary rotations that sequentially maximizes dipole and spin moments through iterative Jacobi sweeps; the resulting update rules are effectively equivalent to those of approximate joint diagonalization (AJD) applied to charge and spin. The method converges rapidly and yields smooth diabatic potential energy surfaces that preserve dipole and spin properties (e.g., a smoothly varying spin quantization axis) along the reaction coordinate while maintaining time-reversal symmetry.

physics.chem-ph↗
arXiv2026

Fixed-Dimensional Latent Flow for Generating Variable-Size 3D Molecules

Molecular size is coupled to composition, structure, and function, yet most 3D molecular generators require a predefined atom count. We introduce Equivariant-Free Transformer-Autoencoded Latent Flow Matching, a two-stage framework that samples a fixed-dimensional latent vector using flow matching and uses an autoregressive Transformer to determine molecular size, atom types, coordinates, and chemical attributes. Canonical atom ordering and rigid-pose alignment enable Transformers without equivariant layers, while decoded attributes guide bond reconstruction. On PCQM4Mv2, unconditional generation yields 87.9\% unique, novel molecules passing sanitization and PoseBusters checks, exceeding baselines with lower end-to-end training and sampling time and higher end-to-end throughput. Across ten target HOMO-LUMO gaps, internal ranking retains 30\% of screened candidates and increases the density functional theory-verified hit rate within 0.1 eV from 25.0\% to 52.4\%, while largely preserving novelty and diversity. These results demonstrate fixed-dimensional latent generation with autoregressive decoding as a practical approach to molecular design without prespecifying size.

physics.chem-ph↗