The W2024 database of the water isotopologue .

The rovibrational spectrum of the water molecule is the crown jewel of high-resolution molecular spectroscopy. While its significance in numerous scientific and engineering applications and the challenges behind its interpretation have been well known, the extensive experimental analysis performed for this molecule, from the microwave to the ultraviolet, is admirable. To determine empirical energy levels for , this study utilizes an improved version of the MARVEL (Measured Active Rotational-Vibrational Energy Levels) scheme, which now takes into account multiplet constraints and first-principles energy-level splittings.

All paths lead to hubs in the spectroscopic networks of water isotopologues HO and HO.

Network theory has fundamentally transformed our comprehension of complex systems, catalyzing significant advances across various domains of science and technology. In spectroscopic networks, hubs are the quantum states involved in the largest number of transitions. Here, utilizing network paths probed via precision metrology, absolute energies have been deduced, with at least 10-digit accuracy, for almost 200 hubs in the experimental spectroscopic networks of HO and HO.

Temperature-Dependent Line-Broadening Effects in CO Caused by Ar.

This computational study of line-broadening effects is based on an accurate, analytical representation of the intermonomer potential energy surface (PES) of the CO  ⋅ Ar van der Waals (vdW) complex. The PES is employed to compute collisional broadening coefficients for rovibrational lines of CO perturbed by Ar. The semiclassical computations are performed using the modified Robert-Bonamy approach, including real and imaginary terms, and the exact trajectory model.

Parity-pair-mixing effects in nonlinear spectroscopy of HDO.

A non-linear spectroscopic study of the HDO molecule is performed in the wavelength range of 1.36-1.42 m using noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy (NICE-OHMS).

Spectroscopic-network-assisted precision spectroscopy and its application to water.

Frequency combs and cavity-enhanced optical techniques have revolutionized molecular spectroscopy: their combination allows recording saturated Doppler-free lines with ultrahigh precision. Network theory, based on the generalized Ritz principle, offers a powerful tool for the intelligent design and validation of such precision-spectroscopy experiments and the subsequent derivation of accurate energy differences. As a proof of concept, 156 carefully-selected near-infrared transitions are detected for HO, a benchmark system of molecular spectroscopy, at kHz accuracy.

Molecular dimers of methane clathrates: ab initio potential energy surfaces and variational vibrational states.

Motivated by the energetic and environmental relevance of methane clathrates, highly accurate ab initio potential energy surfaces (PESs) have been developed for the three possible dimers of the methane and water molecules: (H2O)2, CH4·H2O, and (CH4)2. While only a single monomer geometry was used for each monomer in the ab initio calculations, the PES parameterization makes it possible to produce distinct surfaces for all isotopologues within the rigid-monomer approximation. The PESs were fitted to computations at the frozen-core coupled-cluster level with single, double, and non-iterative triple excitations, employing basis sets of augmented triple- and quadruple-zeta quality plus bond functions, followed by extrapolations to the complete basis set limit.

Accurate empirical rovibrational energies and transitions of HO.

Several significant improvements are proposed to the computational molecular spectroscopy protocol MARVEL (Measured Active Rotational-Vibrational Energy Levels) facilitating the inversion of a large set of measured rovibrational transitions to energy levels. The most important algorithmic changes include the use of groups of transitions, blocked by their estimated experimental (source segment) uncertainties, an inversion and weighted least-squares refinement procedure based on sequential addition of blocks of decreasing accuracy, the introduction of spectroscopic cycles into the refinement process, automated recalibration, synchronization of the combination difference relations to reduce residual uncertainties in the resulting dataset of empirical (MARVEL) energy levels, and improved classification of the lines and energy levels based on their accuracy and dependability. The resulting protocol, through handling a large number of measurements of similar accuracy, retains, or even improves upon, the best reported uncertainties of the spectroscopic transitions employed.

Definitive thermochemistry and kinetics of the interconversions among conformers of n-butane and n-pentane.

The focal-point analysis (FPA) technique is used for the definitive characterization of conformational interconversion parameters, including activation energy barriers, activation free energies, and kinetic rate coefficients at 298 K, of two n-alkanes, n-butane, and n-pentane, yielding the first complete analysis of their interconversion kinetics. The FPA implementation developed in this study is based on geometry optimizations and harmonic frequency computations carried out with density functional theory methods and single-point energy computations up to the CCSD(T) level of electronic structure theory using atom-centered Gaussian basis sets as large as cc-pV5Z. The anharmonic vibrational computations are carried out, at the MP2/6-31G* level of theory.