Hybrid variation-perturbation method for calculating rovibrational energy levels of polyatomic molecules

A procedure for calculation of rotation-vibration states of medium sized molecules is presented. It combines the advantages of variational calculations and perturbation theory. The vibrational problem is solved by diagonalizing a Hamiltonian matrix, which is partitioned into two sub-blocks. The first, smaller sub-block includes matrix elements with the largest contribution to the energy levels targeted in the calculations. The second, larger sub-block comprises those basis states which have little effect on these energy levels. Numerical perturbation theory, implemented as a Jacobi rotation, is used to compute the contributions from the matrix elements of the second sub-block. Only the first sub-block needs to be stored in memory and diagonalized. Calculations of the vibrational-rotational energy levels also employ a partitioning of the Hamiltonian matrix into sub-blocks, each of which corresponds either to a single vibrational state or a set of resonating vibrational states, with all associated rotational levels. Physically, this partitioning is efficient when the Coriolis coupling between different vibrational states is small. Numerical perturbation theory is used to include the cross-contributions from different vibrational states. Separate individual sub-blocks are then diagonalized, replacing the diagonalization of a large Hamiltonian matrix with a number of small matrix diagonalizations. Numerical examples show that the proposed hybrid variational-perturbation method greatly speeds up the variational procedure without significant loss of precision for both vibrational-rotational energy levels and transition intensities. The hybrid scheme can be used for accurate nuclear motion calculations on molecules with up to 15 atoms on currently available computers.Comment: Molecular Physics (Handy Special Issue), in pres

MARVEL analysis of the measured high-resolution rovibronic spectra of the calcium monohydroxide radical (CaOH)

The calcium monohydroxide radical (CaOH) is an important astrophysical molecule relevant to cool stars and rocky exoplanets, amongst other astronomical environments. Here, we present a consistent set of highly accurate rovibronic (rotation-vibration-electronic) energy levels for the five lowest electronic states (\tilde{X}\,^2\Sigma^+, \tilde{A}\,^2\Pi, \tilde{B}\,^2\Sigma^+, \tilde{C}\,^2\Delta, \tilde{D}\,^2\Sigma^+) of CaOH. A comprehensive analysis of the published spectroscopic literature on this system has allowed 1955 energy levels to be determined from 3204 rovibronic experimental transitions, all with unique quantum number labelling and measurement uncertainties. The dataset covers rotational excitation up to $J=62.5$ for molecular states below 29\,000~cm$^{-1}$. The analysis was performed using the MARVEL algorithm, which is a robust procedure based on the theory of spectroscopic networks. The dataset provided will significantly aid future interstellar, circumstellar and atmospheric detections of CaOH, as well as assisting in the design of efficient laser cooling schemes in ultracold molecule research and precision tests of fundamental physics

ExoMol molecular line lists - XVI: The rotation-vibration spectrum of hot H2_2S

This work presents the AYT2 line list: a comprehensive list of 114 million $^{1}$H$_2$$^{32}$S vibration-rotation transitions computed using an empirically-adjusted potential energy surface and an {\it ab initio} dipole moment surface. The line list gives complete coverage up to 11000 \cm\ (wavelengths longer than 0.91 $\mu$m) for temperatures up to 2000 K. Room temperature spectra can be simulated up to 20000 \cm\ (0.5 $\mu$m) but the predictions at visible wavelengths are less reliable. AYT2 is made available in electronic form as supplementary data to this article and at \url{www.exomol.com}.Comment: 12 pages, 10 figures, 10 table

Collective modes of two-dimensional classical Coulomb fluids

Molecular dynamics simulations have been performed to investigate in detail collective modes spectra of two-dimensional Coulomb fluids in a wide range of coupling. The obtained dispersion relations are compared with theoretical approaches based on quasi-crystalline approximation (QCA), also known as the quasi-localized charge approximation (QLCA) in the plasma-related context. An overall satisfactory agreement between theory and simulations is documented for the longitudinal mode at moderate coupling and in the long-wavelength domain at strong coupling. For the transverse mode, satisfactory agreement in the long-wavelength domain is only reached at very strong coupling, when the cutoff wave-number below which shear waves cannot propagate becomes small. The dependence of the cutoff wave-number for shear waves on the coupling parameter is obtained.Comment: 10 pages, 6 figure

A near infrared line list for \NH: Analysis of a Kitt Peak spectrum after 35 years

A Fourier Transform (FT) absorption spectrum of room temperature NH3 in the region 7400 - 8600 cm-1 is analysed using a variational line list and ground state energies determined using the MARVEL procedure. The spectrum was measured by Dr Catherine de Bergh in 1980 and is available from the Kitt Peak data center. The centers and intensities of 8468 ammonia lines were retrieved using a multiline fitting procedure. 2474 lines are assigned to 21 bands providing 1692 experimental energies in the range 7000 - 9000 cm-1. The spectrum was assigned by the joint use of the BYTe variational line list and combination differences. The assignments and experimental energies presented in this work are the first for ammonia in the region 7400 - 8600 cm-1, considerably extending the range of known vibrational-excited statesComment: 27 pages, 6 table, 5 figures. Accepted for publication in Journal of Molecular Spectroscop

First observation of electric-quadrupole infrared transitions in water vapour

Molecular absorption of infrared radiation is generally due to ro-vibrational electric-dipole transitions. Electric-quadrupole transitions may still occur, but they are typically a million times weaker than electric-dipole transitions, rendering their observation extremely challenging. In polyatomic or polar diatomic molecules, ro-vibrational quadrupole transitions have never been observed. Here, we report the first direct detection of quadrupole transitions in water vapor. The detected quadrupole lines have intensity largely above the standard dipole intensity cut-off of spectroscopic databases and thus are important for accurate atmospheric and astronomical remote sensing

ExoMol line lists -- XLI. High-temperature molecular line lists for the alkali metal hydroxides KOH and NaOH

Potassium hydroxide (KOH) and sodium hydroxide (NaOH) are expected to occur in the atmospheres of hot rocky super-Earth exoplanets but a lack of spectroscopic data is hampering their potential detection. Using robust first-principles methodologies, comprehensive molecular line lists for KOH and NaOH that are applicable for temperatures up to $T=3500$ K are presented. The KOH OYT4 line list covers the 0-6000 cm$^{-1}$ (wavelengths $\lambda > 1.67$ $\mu$m) range and comprises 38 billion transitions between 7.3 million energy levels with rotational excitation up to $J=255$. The NaOH OYT5 line list covers the 0 - 9000 cm$^{-1}$ (wavelengths $\lambda > 1.11$ $\mu$m) range and contains almost 50 billion lines involving 7.9 million molecular states with rotational excitation up to $J=206$. The OYT4 and OYT5 line lists are available from the ExoMol database at www.exomol.com and should greatly aid the study of hot rocky exoplanets

ExoMol molecular line lists XXX: a complete high-accuracy line list for water

A new line list for H$_2$$^{16}$O is presented. This line list, which is called POKAZATEL, includes transitions between rotation-vibrational energy levels up to 41000 cm$^{-1}$ in energy and is the most complete to date. The potential energy surface (PES) used for producing the line list was obtained by fitting a high-quality ab initio PES to experimental energy levels with energies of 41000 cm$^{-1}$ and for rotational excitations up to $J=5$. The final line list comprises all energy levels up to 41000 cm$^{-1}$ and rotational angular momentum $J$ up to 72. An accurate ab initio dipole moment surface (DMS) was used for the calculation of line intensities and reproduces high-precision experimental intensity data with an accuracy close to 1 %. The final line list uses empirical energy levels whenever they are available, to ensure that line positions are reproduced as accurately as possible. The POKAZATEL line list contains over 5 billion transitions and is available from the ExoMol website (www.exomol.com) and the CDS database