Kraitchman has shown that a single isotopic substitution on an atom is sufficient to determine directly the coordinates of that atom with respect to the principal axes of the original molecule. Kraitchman's formulas represent exact solutions of the equations for the equilibrium moments of inertia. However, the effects of the zero‐point vibrations are such that the coordinates obtained by substitution from the ground state moments of inertia I0 are systematically less than r0. These coordinates have here been called r (substitution) or rs, and it is found that rs≃(r0+re)/2, and Is= ∑ imirsi2≃(I0+Ie)/2.In the usual method of solution, the coordinate of one atom is determined from the equation for I0, and therefore the difference I0—Is must be made up by this one coordinate. This introduces a large error in the structures normally determined from ground state constants, and results in variations of 0.01 A in structures determined from different sets of isotopic species. If instead, we obtain the structure on...

A new criterion for the determination of molecular structures from ground state rotational constants

In this paper, we present mean gas and dust opacities relevant to the physical conditions typical of protoplanetary discs. As the principal absorber for temperatures below ∼1500 K, we consider spherical and aggregate dust particles of various sizes, chemical structure, and porosity, consisting of ice, organics, troilite, silicates, and iron. For higher temperatures, ions, atoms, molecules, and electrons are included as the main opacity sources. Rosseland and Planck mean opacities are calculated for temperatures between 5 K and 10 000 K and gas densities ranging from 10 −18 gc m −3 to 10 −7 gc m −3 . The dependence on the adopted model of dust grains is investigated. We compare our results with recent opacity tables and show how different opacity models affect the calculated hydrodynamical structure of accretion discs.

https://www.aanda.org/articles/aa/pdf/2003/41/aa3802.pdf

Rosseland and Planck mean opacities for protoplanetary discs

We present a comparative assessment of the performance of the M06 suite of density functionals (M06, M06-2X, and M06-HF) against an MP2 benchmark for calculating the relative energies and geometric structures of the Cl(-)·arginine and Br(-)·arginine halide ion-amino acid clusters. Additional results are presented for the popular B3LYP density functional. The Cl(-)·arginine and Br(-)·arginine complexes are important prototypes for the phenomenon of anion-induced zwitterion formation. Results are presented for the canonical (noncharge separated) and zwitterionic (charge separated) tautomers of the clusters, as well as the numerous conformational isomers of the clusters. We find that all of the M06 functions perform well in terms of predicting the general trends in the conformer relative energies and identifying the global minimum conformer. This is in contrast to the B3LYP functional, which performed significantly less well for the canonical tautomers of the clusters where dispersion interactions contribute more significantly to the conformer energetics. We find that the M06 functional gave the lowest mean unsigned error for the relative energies of the canonical conformers (2.10 and 2.36 kJ/mol for Br(-)·arginine and Cl(-)·arginine), while M06-2X gave the lowest mean unsigned error for the zwitterionic conformers (0.85 and 1.23 kJ/mol for Br(-)·arginine and Cl(-)·arginine), thus providing insight into the types of physical systems where each of these functionals should perform best.

Performance of M06, M06-2X, and M06-HF density functionals for conformationally flexible anionic clusters: M06 functionals perform better than B3LYP for a model system with dispersion and ionic hydrogen-bonding interactions.

1. General introduction 2. The separation of nuclear and electronic motion 3. The electronic hamiltonian 4. Interactions arising from nuclear magnetic and electric moments 5. Angular momentum theory and spherical tensor algebra 6. Electronic and vibrational states 7. Derivation of the effective hamiltonian 8. Molecular beam magnetic and electric resonance 9. Microwave and far-infrared magnetic resonance 10. Pure rotational spectroscopy 11. Double resonance spectroscopy Appendices.

https://physicstoday.scitation.org/doi/pdf/10.1063/1.1878342

Rotational Spectroscopy of Diatomic Molecules

to Planar Systems Tadeusz M. Krygowski,*,† Halina Szatylowicz,*,‡ Olga A. Stasyuk,‡ Justyna Dominikowska, and Marcin Palusiak †Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland ‡Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland Department of Theoretical and Structural Chemistry, Faculty of Chemistry, University of Łod́z,́ Pomorska 163/165, 90-236 Łod́z,́ Poland

Aromaticity from the viewpoint of molecular geometry: application to planar systems.

Rotational spectroscopy in combination with molecular beams and laser ablation (laser-ablation molecular-beam Fourier transform microwave (LA-MB-FTMW) spectroscopy) has proved to be successful in characterizing the conformers of natural amino acids. The procedure usually followed to assign and identify the different conformers of an amino acid from the rotational spectrum is described through the study of the natural amino acidL-threonine. The solid sample of L-threonine was vaporized by laser pulses, diluted in Ne and supersonically expanded between the mirrors of a Fabry–Perot resonator where it was spectroscopically probed by microwave radiation. The rotational and nuclear quadrupole coupling constants extracted from the analysis of the rotational spectrum are directly compared with those predicted by ab initio methods to achieve the conclusive identification of seven different conformers. A complex hydrogen bonding network arises as a consequence of the polar side chain of threonine.

Seven conformers of L-threonine in the gas phase: a LA-MB-FTMW study.

The glycine-water complex.

We explored the conformational landscape of the proteinogenic amino acid serine [CH2OHCH(NH2)COOH] in the gas phase. Solid serine was vaporized by laser ablation, expanded in a supersonic jet, and characterized by Fourier transform microwave spectroscopy. In the isolation conditions of the jet there have been discovered up to seven different neutral (non-zwitterionic) structures of serine, which are conclusively identified by the comparison between the experimental values of the rotational and quadrupole coupling constants with those predicted by ab initio calculations. These seven forms can serve as a basis to represent the shape of serine in the gas phase. From the postexpansion abundances we derived the conformational stability trend, which is controlled by the subtle network of intramolecular hydrogen bonds formed between the polar groups in the amino acid backbone and the hydroxy side chain. It is proposed that conformational cooling perturbs the equilibrium conformational distribution; thus, some of the lower-energy forms are “missing” in the supersonic expansion.

https://www.pnas.org/content/pnas/104/51/20183.full.pdf

Revealing the multiple structures of serine.

The combination of Fourier transform microwave spectroscopy in a pulsed supersonic jet with laser ablation has made beta-alanine amenable to a structural study in the gas phase. Two new conformers of beta-alanine have been identified together with the two previously observed by McGlone and Godfrey [J. Am. Chem. Soc. 1995, 117, 1043]. The comparison between the experimental rotational and 14N nuclear quadrupole coupling constants and those calculated ab initio provide a definitive test for molecular structures and confirm unambiguously the identification of all conformers. For the two most abundant conformers, an intramolecular hydrogen bond between the amino group and carbonyl oxygen (N-H...O=C) is established, and the COOH adopts a cis-COOH configuration. The next conformer in order of abundance presents an O-H...N intramolecular hydrogen bond with a trans configuration for the COOH group. The high sensitivity of the experiment has allowed us to detect for the first time a conformer uniquely stabilized by an n-pi* hyperconjugative interaction between the nucleophile N: of the amino group and the pi* orbital at the carbonyl group. Partial conformational relaxation has been observed in the supersonic expansion.

The shape of beta-alanine.

has made possible the gas-phase study of solidbiomolecules with high melting points. In this approach,solidsarevaporizedbyahigh-energylaserpulse,supersoni-callyexpandedintoavacuumchamber,andcharacterizedbytheirrotationalspectrum.Ofthebiomoleculesthathavebeenstudiedbythistechnique,aliphaticaminoacidshavereceivedspecial attention because of the lack of experimental infor-mationandtheirbiologicalrelevance.Aminoacidsarewellknowntoexistaszwitterions(NH

M. Eugenia Sanz

Papers

Seven conformers of L-threonine in the gas phase: a LA-MB-FTMW study.

The glycine-water complex.

Revealing the multiple structures of serine.

The shape of beta-alanine.

Rotational Probes of Six Conformers of Neutral Cysteine