Supplementary information: The nuclear-spin-forbidden rovibrational transitions of water from first principles

<strong>Supplementary material to the manuscript <em>"The nuclear-spin-forbidden rovibrational transitions of water from first principles"</em> by Andrey Yachmenev, Guang Yang, Emil Zak, Sergei Yurchenko, and Jochen Küpper, <em>J. Chem. Phys., submitted. </em></strong> arXiv:2203.07945 The data set contains hyperfine (spin-rovibrational) energies and dipole transition spectrum of water molecule (H₂¹⁶O), calculated using variational approach TROVE and RichMol, and included spin-rotational and spin-spin hyperfine interactions. In addition, the data set includes HDF5-type richmol database file <strong><em>h2o_p48_j40_rovib.h5</em></strong> (see https://github.com/CFEL-CMI/richmol) containing rovibrational energies, matrix elements of nuclear spin-rotation, nuclear spin-spin, electric dipole, and electric quadrupole tensor operators of H₂¹⁶O, calculated using variational approach TROVE. <strong>h2o_exomol_F.states </strong>and<strong> h2o_exomol_F.trans</strong> - hyperfine linelist of water stored in the ExoMol format (see, e.g., J. Molec. Spectrosc., 327, 73-94 (2016)). The two files contain a set of hyperfine states with assignments and a set of dipole transitions (Einstein A-coefficients), respectively. The states in <strong>h2o_exomol_F.states</strong> file are arranged by quantum number of total angular momentum F = I + J (spin + rotation) in ascending order. <strong>h2o_exomol_J.states </strong>and<strong> h2o_exomol_J.trans</strong> - contain same data as <strong>h2o_exomol_F.states </strong>and<strong> h2o_exomol_F.trans</strong> files, except that the states in <strong>h2o_exomol_J.states</strong> file are arranged by rotational quantum number (J) in ascending order. <strong>h2o_p48_j40_rovib.h5<em> - </em></strong>Richmol HDF5 database file for H₂¹⁶O containing rovibrational energies (in cm^-1), matrix elements of nuclear spin-rotation (in kHz), spin-spin (in kHz), molecular electric dipole moment (in Debye), and molecular electric quadrupole moment (in a.u.) operators. For details on how to read this file, see Richmol GitHub repository and Richmol documentation (<em>or contact Andrey Yachmenev at [e-mail]</em>). <strong>ortho_para_transitions.txt</strong> - table with strongest predicted ortho-para transitions in H₂¹⁶O at T = 296 K with the 10⁻³⁶ cm/molecule intensity cut-off.<br> <br> <strong><em>An example of hyperfine energies and hyperfine dipole spectrum calculation for water using h2o_p48_j40_rovib.h5 file from this repository may be found in the Richmol GitHub repository's examples folder: https://github.com/CFEL-CMI/richmol/tree/develop/examples/hyperfine</em></strong> Structure of<strong> h2o_exomol_F.states </strong>and<strong> h2o_exomol_J.states </strong>files: Column No. Kind Meaning 1 int state ID number 2 float hyperfine state energy relative to the ZPE, in cm^-1 3 int state degeneracy 4 int value of F quantum number (total spin-rotational angular momentum) 5 str state symmetry in C_2v 6 int value of J quantum number (total rotational angular momentum) 7 str symmetry of state's rotational component in C_2v 8 int value of k_a quantum number (a-axis projection of rotational angular momentum) 9 int value of k_c quantum number (c-axis projection of rotational angular momentum) 10 int value of v₁ vibrational quantum number 11 int value of v₂ vibrational quantum number 12 int value of v₃ vibrational quantum number 13 int value of I quantum number (total nuclear spin) 14 float reference rovibrational state energy (i.e., without hyperfine effects) relative to the ZPE, in cm^-1 Structure of<strong> h2o_exomol_F.trans </strong>and<strong> h2o_exomol_J.trans </strong>files: Column No. Kind Meaning 1 int ID number of final transition state (col. no. 1 in <strong>h2o_exomol_F.states </strong>or<strong> h2o_exomol_J.states </strong>file) 2 int ID number of initial transition state (col. no. 1 in <strong>h2o_exomol_F.states </strong>or<strong> h2o_exomol_J.states </strong>file) 3 float Einstein A-coefficient, in s^-1 4 float Transition wavenumber, in cm^-1