Search arXiv⌕ Search
Home/Archive/arXiv

arXiv · 1809.08540

Time-resolved double-resonance spectroscopy: Lifetime measurement of the $6\,^1Σ_g^+(7,31)$ electronic state of molecular sodium

Michael Saaranen·Dinesh Wagle·Emma McLaughlin·Amelia Paladino·Seth Ashman·S. Burcin Bayram
View original source ↗Read source document ↗Export metadata ↓

Abstract

We report on the lifetime measurement of the $6\,^1Σ_g^+ (7,31)$ state of Na$_2$ molecules, produced in a heat-pipe oven, using a time-resolved spectroscopic technique. The $6\,^1Σ_g^+ (7,31)$ level was populated by two-step two-color double resonance excitation via the intermediate $A\,^1Σ_u^+ (8,30)$ state. The excitation scheme was done using two synchronized pulsed dye lasers pumped by a Nd:YAG laser operating at the second harmonics. The fluorescence emitted upon decay to the final state was measured using a time-correlated photon counting technique, as a function of argon pressure. From this the radiative lifetime was extracted by extrapolating the plot to collision-free zero pressure. We also report calculated radiative lifetimes of the Na$_2$ $6\,^1Σ_g^+$ ro-vibrational levels in the range of $v=0-200$ with $J=1$ and $J=31$ using the LEVEL program for bound-bound and the BCONT program for bound-free transitions. Our calculations reveal the importance of the bound-free transitions on the lifetime calculations and a large difference of about a factor of three between the $J=1$ and $J=31$ for the $v=40$ and $v=100$, due to the wavefunction alternating between having predominantly inner and outer well amplitude.

Explore related subjects

physics.chem-phphysics.atm-clus

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Michael Saaranen, Dinesh Wagle, Emma McLaughlin, Amelia Paladino, Seth Ashman, S. Burcin Bayram. 2018-09-23. Time-resolved double-resonance spectroscopy: Lifetime measurement of the $6\,^1Σ_g^+(7,31)$ electronic state of molecular sodium. https://doi.org/10.1063/1.5061729

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↗