Search arXivSearch

arXiv · 2412.07311

Precision frequency comb spectroscopy of the $^{14}$N$_{2}$O, $^{14}$N$^{15}$NO, $^{15}$N$^{14}$NO, and $^{15}$N$_{2}$O isotopocules in the 3300-3550 cm$^{-1}$ range

Abstract

Nitrous oxide is a long-lived greenhouse gas. Its isotopic composition provides valuable insights into sources and sinks, and about the mechanism of formation. A major challenge in the spectroscopic analysis of the isotopocule compositions is the availability of accurate spectroscopic parameters, particularly for the minor $^{15}$N isotopocules. In this work, we introduce high-resolution spectroscopic measurements of four isotopocules of nitrous oxide: $^{14}$N$_{2}$O, $^{14}$N$^{15}$NO, $^{15}$N$^{14}$NO, and $^{15}$N$_{2}$O in the mid-infrared range of 3300 - 3550 cm$^{-1}$, using a frequency comb-based Fourier transform spectrometer. The nitrous oxide samples were obtained from a chemical synthesis involving acid-catalyzed amine-borane reduction of equimolar amounts of $^{15}$N isotopically enriched sodium nitrite and $^{14}$N sodium nitrite. The high-resolution spectra, measured in a temperature-controlled single-pass absorption cell, were used to retrieve line center frequencies and relative intensities for a total of 426 rovibrational transitions of the $ν$$_{1}$ + $ν$$_{3}$ band of the four isotopocules, and of the one order of magnitude weaker 2$ν$$_{2}$ + $ν$$_{3}$ and $ν$$_{1}$ + $ν$$_{2}$ + $ν$$_{3}$ - $ν$$_{2}$ bands in the same spectral region. We compare the determined line center frequencies and relative intensities with spectroscopic parameters available in high-resolution molecular databases. For $^{14}$N$_{2}$O, $^{14}$N$^{15}$NO and $^{15}$N$^{14}$NO we find good agreement with the HITRAN database. The $^{15}$N$_{2}$O isotopocule is missing in HITRAN, and we find that its line center frequencies in the GEISA database, the Institute of Atmospheric Optics database, as well as the Ames-1 line list deviate severely from the comb measurements.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Adrian Hjältén, Ibrahim Sadiek, Aleksandra Foltynowicz. 2024-12-10. Precision frequency comb spectroscopy of the $^{14}$N$_{2}$O, $^{14}$N$^{15}$NO, $^{15}$N$^{14}$NO, and $^{15}$N$_{2}$O isotopocules in the 3300-3550 cm$^{-1}$ range. https://doi.org/10.1016/j.jqsrt.2025.109452

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

KEEP EXPLORING

Related papers

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

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

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