General Perturbative Approach for Spectroscopy, Thermodynamics, and Kinetics: Methodological Background and Benchmark Studies (Articolo in rivista)

Type
Label
  • General Perturbative Approach for Spectroscopy, Thermodynamics, and Kinetics: Methodological Background and Benchmark Studies (Articolo in rivista) (literal)
Anno
  • 2012-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/ct200814m (literal)
Alternative label
  • Bloino, Julien; Biczysko, Malgorzata; Barone, Vincenzo (2012)
    General Perturbative Approach for Spectroscopy, Thermodynamics, and Kinetics: Methodological Background and Benchmark Studies
    in Journal of chemical theory and computation
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Bloino, Julien; Biczysko, Malgorzata; Barone, Vincenzo (literal)
Pagina inizio
  • 1015 (literal)
Pagina fine
  • 1036 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 8 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 22 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
  • 3 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Scuola Normale Superiore, piazza dei Cavalieri 7, I-56126 Pisa (Italy); Center for Nanotechnology Innovation @NEST, Istituto Italiano di Tecnologia, Piazza San Silvestro 12, I-56127 Pisa (Italy); Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), UOS di Pisa, Via G. Moruzzi, 1 I-56124 Pisa (Italy) (literal)
Titolo
  • General Perturbative Approach for Spectroscopy, Thermodynamics, and Kinetics: Methodological Background and Benchmark Studies (literal)
Abstract
  • A general second-order perturbative approach based on resonance- and threshold-free computations of vibrational properties is introduced and validated. It starts from the evaluation of accurate anharmonic zero-point vibrational energies for semirigid molecular systems, in a way that avoids any singularity. Next, the degeneracy corrected second-order perturbation theory (DCPT2) is extended to a hybrid version (HDCPT2), allowing for reliable computations even in cases where the original formulation faces against severe problems, including also an automatic treatment of internal rotations through the hindered-rotor model. These approaches, in conjunction with the so-called simple perturbation theory (SPT) reformulated to treat consistently both energy minima and transition states, allow one to evaluate degeneracy-corrected partition functions further used to obtain vibrational contributions to properties like enthalpy, entropy, or specific heat. The spectroscopic accuracy:of the HDCPT2 model has been also validated by computing anharmonic vibrational frequencies for a number of small-to-medium size, closed- and open-shell, molecular systems, within an accuracy close to that of well established but threshold-dependent perturbative-variational models. The reliability of the B3LYP/aug-N07D model for anharmonic computations is also highlighted, with possible improvements provided by the B2PLYP/aug-cc-pVTZ models or by hybrid schemes. On a general grounds, the overall approach proposed in the present work is able to provide the proper accuracy to support experimental investigations even for large molecular systems of biotechnological interest in a fully automated manner, without any ad hoc scaling procedure. This means a fully ab initio evaluation of thermodynamic and spectroscopic properties with an overall accuracy of about, or better than, 1 kJ mol^(-1), 1 J mol^(-1) K-1 and 10 cm^(-1) for enthalpies, entropies, and vibrational frequencies, respectively. (literal)
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