This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is composed of five major components: the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, collision-induced absorption data, aerosol indices of refraction, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, added line-shape formalisms, and validity. Moreover, molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth. Of considerable note, experimental IR cross-sections for almost 300 additional molecules important in different areas of atmospheric science have been added to the database. The compilation can be accessed through www.hitran.org. Most of the HITRAN data have now been cast into an underlying relational database structure that offers many advantages over the long-standing sequential text-based structure. The new structure empowers the user in many ways. It enables the incorporation of an extended set of fundamental parameters per transition, sophisticated line-shape formalisms, easy user-defined output formats, and very convenient searching, filtering, and plotting of data. A powerful application programming interface making use of structured query language (SQL) features for higher-level applications of HITRAN is also provided.

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The HITRAN 2008 molecular spectroscopic database

We present an approach for deriving net atomic charges from ab initio quantum mechanical calculations using a least squares fit of the quantum mechanically calculated electrostatic potential to that of the partial charge model. Our computational approach is similar to those presented by Momany [J. Phys. Chem., 82, 592 (1978)], Smit, Derissen, and van Duijneveldt [Mol. Phys., 37, 521 (1979)], and Cox and Williams [J. Comput. Chem., 2, 304 (1981)], but differs in the approach to choosing the positions for evaluating the potential. In this article, we present applications to the molecules H2O, CH3OH, (CH3)2O, H2CO, NH3, (CH3O)2PO, deoxyribose, ribose, adenine, 9-CH3 adenine, thymine, 1-CH3 thymine, guanine, 9-CH3 guanine, cytosine, 1-CH3 cytosine, uracil, and 1-CH3 uracil. We also address the question of inclusion of “lone pairs,” their location and charge.

An approach to computing electrostatic charges for molecules

We have carried out a natural bond orbital analysis of hydrogen bonding in the water dimer for the near‐Hartree–Fock wave function of Popkie, Kistenmacher, and Clementi, extending previous studies based on smaller basis sets and less realistic geometry. We find that interactions which may properly be described as ‘‘charge transfer’’ (particularly the n‐σ*OH interaction along the H‐bond axis) play a critical role in the formation of the hydrogen bond, and without these interactions the water dimer would be 3–5 kcal/mol repulsive at the observed equilibrium distance. We discuss this result in relationship to Klemperer’s general picture of the bonding in van der Waals molecules, and to previous theoretical analyses of hydrogen bonding by the method of Kitaura and Morokuma.

Natural bond orbital analysis of near‐Hartree–Fock water dimer

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

The Halogen Bond

Before we start, we need a working definition for MOPAC. The following description has been used many times to describe MOPAC: MOPAC is a general-purpose, semiempirical molecular orbital program for the study of chemical reactions involving molecules, ions, and linear polymers. It implements the semiempirical Hamiltonians MNDO, AM 1, MINDO/3, and MNDOPM3, and combir_es the calculations of vibrational spectra, thermodynamic quantities, isotopic substitution effects, and force constants in a fully integrated program. Elements parameterized at the MNDO level include H, Li, Be, B, C, N, O, F, A1, Si, P, S, C1, Ge, Br, Sn, Hg, Pb, and I; at the PM3 level the elements H, C, N, O, F, A1, Si, P, S, C1, Br, and I are available. Within the electronic part of the calculation, molecular and localized orbitals, excited states up to sextets, chemical bond indices, charges, etc. are computed. Both intrinsic and dynamic reaction coordinates can be calculated. A transition-state location routine and two transition-state optimizing routines are available for studying chemical reactions.

MOPAC: A semiempirical molecular orbital program

We describe the design, construction, and operation of a new type of microwave spectrograph which allows the measurement of the resonant transitions of transient or otherwise short‐lived species. The spectrograph is composed of three parts: a Fabry–Perot cavity, a pulsed supersonic nozzle as a source for the sample, and the pulsed microwave Fourier transform method. Following a detailed discussion of the three above components in the spectrograph, the operation of the entire system is described and several examples are given.

Fabry–Perot cavity pulsed Fourier transform microwave spectrometer with a pulsed nozzle particle source

We have measured the dispersion of the gas phase depolarization ratio of Rayleigh scattered light for 12 linear and symmetric top molecules Combining these data with known refractive index data we obtain the frequency dependence of the polarizability anisotropy For all molecules studied we find that the polarizability anisotropy increases more rapidly with increasing frequency than the bulk polarizability We have correlated this behavior with the oscillator strength and direction of the first electronic transition We have also compared our zero frequency extrapolated anisotropies with the anisotropies determined from static fields with the Kerr effect and the Stark effect in microwave spectroscopy

Measurement of the dispersion in polarizability anisotropies

The outer s‐ and p‐electron overlap integrals involving ns, npσ, and npπ orbitals have been computed for all combinations of ion pairs in all of the alkali halide lattices. The free‐ion closed‐shell Hartree—Fock wavefunctions were used in all calculations. The halogen—alkali (H—M) overlaps are listed at the equilibrium internuclear distances. The halogen—alkali (H—M), halogen—halogen (H–H), and alkali—alkali (M—M) overlap integrals were computed at several internuclear distances and were found to follow the exponential form Sab=A exp(—rab/ρ). Values of A and ρ are listed for all combinations of overlaps in the alkali halides.Various convenient combinations of sums of squares of overlaps are also given as a function of distance for all the combinations in the alkali halide lattices.

Outer‐Shell Overlap Integrals as a Function of Distance for Halogen—Halogen, Halogen—Alkali, and Alkali—Alkali Ions in the Alkali Halide Lattices

Equations are derived relating the spin—rotation constants and magnetic shielding for any type of molecule. In general, the spin—rotation constants depend on the equilibrium nuclear positions and a second‐order term involving the excited electronic states. The spin—rotation constants are interpreted by a localized theory in terms of the average excitation energy, average value of (1/r3), and the charge‐bond order matrix of the associated LCAO—MO functions.

Spin—Rotation Interaction and Magnetic Shielding in Molecules

A new method of observing the rotational transitions of weak molecular complexes by combining the techniques of microwave Fourier transform spectroscopy, a Fabry–Perot cavity, and a pulsed nozzle source of molecules is described. High resolution and good sensitivity are achieved. Twelve isotopic species of the KrHCl molecule involving all combinations of the 86Kr, 84Kr, 82Kr, H, D, 35Cl, and 37Cl isotopes are assigned and the rotational constants, Cl nuclear quadrupole coupling constants, and centrifugal distortion constants are all given. The molecular structure indicates a linear equilibrium structure with the H(D) atom between the Kr and Cl atoms. However, the inverse moments of inertia measured here indicate large amplitude vibrations of the H(D) atom relative to the Kr–Cl internuclear line. Estimates of the Kr–Cl stretching frequency and force constants, which show considerable dependence on the isotopic species, are also given. Bending frequencies and force constants are also given.

W. H. Flygare

Papers

Fabry–Perot cavity pulsed Fourier transform microwave spectrometer with a pulsed nozzle particle source

Measurement of the dispersion in polarizability anisotropies

Outer‐Shell Overlap Integrals as a Function of Distance for Halogen—Halogen, Halogen—Alkali, and Alkali—Alkali Ions in the Alkali Halide Lattices

Spin—Rotation Interaction and Magnetic Shielding in Molecules

A new method for observing the rotational spectra of weak molecular complexes: KrHCl