Wydział Chemii

Vincenzo Barone

Małgorzata Biczysko

Julien Bloino

Cristina Puzzarini

2013

Journal of Chemical Theory and Computation

9

1533-1547

10.1021/ct3010672

Naukowa

Angielski

Artykuł

A state-of-the-art computational strategy for the evaluation of accurate molecular structures as well as thermodynamic and spectroscopic properties along with the direct simulation of infrared (IR) and Raman spectra is established, validated (on the basis of the experimental data available for the Ip glycine conformer) and then used to provide a reliable and accurate characterization of the elusive IVn/gtt and IIIp/tct glycine conformers. The integrated theoretical model proposed is based on accurate post-Hartree–Fock computations (involving composite schemes) of energies, structures, properties, and harmonic force fields coupled to DFT corrections for the proper inclusion of vibrational effects at an anharmonic level (as provided by general second-order perturbative approach). It is shown that the approach presented here allows the evaluation of structural, thermodynamic, and spectroscopic properties with an overall accuracy of about, or better than, 0.001 Å, 20 MHz, 1 kJ·mol^–1, and 10 cm^–1 for bond distances, rotational constants, conformational enthalpies, and vibrational frequencies, respectively. The high accuracy of the computational results allows one to support and complement experimental studies, thus providing (i) an unequivocal identification of several conformers concomitantly present in the experimental mixture and (ii) data not available or difficult to experimentally derive.

Basis sets, Energy, Infrared light, Molecular structure

http://dx.doi.org/10.1021/ct3010672

https://www.acs.org/content/acs/en.html